WO2013022102A1

WO2013022102A1 - Ethylene polymerization catalyst and method for producing ethylene polymer

Info

Publication number: WO2013022102A1
Application number: PCT/JP2012/070564
Authority: WO
Inventors: 正人 ▲高▼野; 伊藤　和幸; 昭彦石井; 憲男中田; 史彦河内; 智之戸田
Original assignee: 住友化学株式会社; 国立大学法人埼玉大学
Priority date: 2011-08-11
Filing date: 2012-08-10
Publication date: 2013-02-14

Abstract

Provided is a catalyst containing a complex represented by general formula (1), and capable of synthesizing an ethylene polymer by catalyzing an ethylene homopolymer or a copolymer of ethylene and α-olefin, wherein the polymer obtained has high activity and a higher molecular weight.

Description

Ethylene-based polymerization catalyst and method for producing ethylene-based polymer

The present invention relates to a catalyst for ethylene homopolymerization or ethylene and α-olefin copolymer using a hafnium complex, and a method for producing an ethylene polymer or ethylene and α-olefin copolymer.

In recent years, the development of metallocene catalysts has been one of the topics in the chemistry of olefin polymerization that has been greatly developed by Ziegler-Natta type magnesium-supported highly active titanium catalysts. Further, recently, development of so-called post metallocene catalysts has attracted attention as a catalyst for constructing a more precise polymerization process.

In 2000, Kol et al. Developed a zirconium complex having C ₂ symmetry by using a tetradentate ligand having a phenoxy group having a high affinity with a group 4 metal element and a nitrogen atom, and using this as a catalyst 1 -Reported the polymerization reaction of hexene (Non-Patent Documents 1 to 3). Furthermore, Kol (Non-Patent Document 4) and Okuda et al. (Non-Patent Documents 5 and 6) in Germany have proposed a group 4 metal complex using a ligand in which the nitrogen atom of the tetradentate ligand is replaced with a sulfur atom. It has been synthesized and developed for stereoselective polymerization of α-olefins.

Patent Document 1 reports propylene polymerization of diphenoxytitanium, zirconium or hafnium complexes derived from ethane-1,2-dithiol.

The present inventors have reported diphenoxy titanium, zirconium and hafnium complexes derived from trans-cyclooctane-1,2-dithiol (Non-patent Document 7), and among these complexes, the zirconium complex was used as a catalyst. 1-hexene polymerization was reported (Non-patent Document 8).

WO2007 / 075299

An object of the present invention is to provide a catalyst containing a tetradentate postmetallocene complex that is highly active in an ethylene-based polymer, and is capable of synthesizing a higher molecular weight polymer. It is in providing the manufacturing method of the used ethylene-type polymer.

The catalyst according to the present invention is a catalyst for ethylene homopolymerization or ethylene and α-olefin copolymer containing a complex represented by the following general formula (1).

(Wherein n is 2 or 3,
R ¹ and R ⁵ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms constituting the ring, an alkenyl group having 2 to 20 carbon atoms, Alkynyl group having 2 to 20 carbon atoms, aralkyl group having 7 to 30 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aralkyloxy group having 7 to 30 carbon atoms, aryloxy having 6 to 30 carbon atoms Group, or a hydrocarbylsilyl group having 1 to 20 carbon atoms,
R ² to R ⁴ and R ⁶ to R ¹² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms constituting the ring, carbon An alkenyl group having 2 to 20 atoms, an alkynyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, carbon Aralkyloxy group having 7 to 30 atoms, aryloxy group having 6 to 30 carbon atoms, hydrocarbylsilyl group having 1 to 20 carbon atoms, or heterocyclic having 3 to 20 carbon atoms constituting the ring Represents a compound residue,
The alkyl group, the cycloalkyl group, the alkenyl group, the aryl group, the alkoxy group, the aralkyloxy group, the aryloxy group, the hydrocarbylsilyl group, and the heterocyclic compound residue in R ¹ to R ¹² The group may have a substituent,
R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁹ and R ¹⁰ , and R ¹¹ and R ¹² , Each independently may be linked together to form a ring,
The two Ls are each independently a hydrogen atom, a halogen atom, an amino group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms constituting the ring, or 2 to 20 alkenyl groups, aralkyl groups having 7 to 30 carbon atoms, aryl groups having 6 to 30 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aralkyloxy groups having 7 to 30 carbon atoms, 6 carbon atoms An aryloxy group having 1 to 30 carbon atoms, a hydrocarbylsilyl group having 1 to 20 carbon atoms, a hydrocarbylamino group having 1 to 20 carbon atoms, a hydrocarbylthiolate group having 1 to 20 carbon atoms, or the number of carbon atoms Represents 1 to 20 carboxylate groups. The alkyl group, the cycloalkyl group, the alkenyl group, the aralkyl group, the aryl group, the alkoxy group, the aralkyloxy group, the aryloxy group, the hydrocarbylsilyl group, the hydrocarbylamino group in L The hydrocarbyl thiolate group and the carboxylate group may have a substituent. )
The method for producing an ethylene polymer according to the present invention is a method for producing an ethylene polymer in which ethylene is polymerized alone or ethylene and an α-olefin are copolymerized in the presence of the above-described catalyst.

According to the present invention, an ethylene homopolymer or a copolymer of ethylene and α-olefin can be efficiently obtained, and a polymer having a higher molecular weight can be obtained.

The present invention relates to an ethylene homopolymerization catalyst or an ethylene and α-olefin copolymerization catalyst containing a hafnium complex represented by the following general formula (1).

(Wherein n is 2 or 3,
R ¹ and R ⁵ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms constituting the ring, an alkenyl group having 2 to 20 carbon atoms, Alkynyl group having 2 to 20 carbon atoms, aralkyl group having 7 to 30 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aralkyloxy group having 7 to 30 carbon atoms, aryloxy having 6 to 30 carbon atoms Group, or a hydrocarbylsilyl group having 1 to 20 carbon atoms,
R ² to R ⁴ and R ⁶ to R ¹² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms constituting the ring, carbon An alkenyl group having 2 to 20 atoms, an alkynyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, carbon Aralkyloxy group having 7 to 30 atoms, aryloxy group having 6 to 30 carbon atoms, hydrocarbylsilyl group having 1 to 20 carbon atoms, or heterocyclic having 3 to 20 carbon atoms constituting the ring Represents a compound residue,
The alkyl group, the cycloalkyl group, the alkenyl group, the aryl group, the alkoxy group, the aralkyloxy group, the aryloxy group, the hydrocarbylsilyl group, and the heterocyclic compound residue in R ¹ to R ¹² The group may have a substituent, and R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁹ and R ¹⁰ , and R ¹¹ and R ¹² may be independently connected to each other to form a ring,
The two Ls are each independently a hydrogen atom, a halogen atom, an amino group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms constituting the ring, or 2 to 20 alkenyl groups, aralkyl groups having 7 to 30 carbon atoms, aryl groups having 6 to 30 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aralkyloxy groups having 7 to 30 carbon atoms, 6 carbon atoms An aryloxy group having 1 to 30 carbon atoms, a hydrocarbylsilyl group having 1 to 20 carbon atoms, a hydrocarbylamino group having 1 to 20 carbon atoms, a hydrocarbylthiolate group having 1 to 20 carbon atoms, or the number of carbon atoms Represents 1 to 20 carboxylate groups. The alkyl group, the cycloalkyl group, the alkenyl group, the aralkyl group, the aryl group, the alkoxy group, the aralkyloxy group, the aryloxy group, the hydrocarbylsilyl group, the hydrocarbylamino group in L The hydrocarbyl thiolate group and the carboxylate group may have a substituent. )
In the above general formula (1), n is 2 or 3, preferably 3.

R ¹ and R ⁵ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms constituting the ring, an alkenyl group having 2 to 20 carbon atoms, Alkynyl group having 2 to 20 carbon atoms, aralkyl group having 7 to 30 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aralkyloxy group having 7 to 30 carbon atoms, aryloxy having 6 to 30 carbon atoms Or a hydrocarbylsilyl group having 1 to 20 carbon atoms. R ² to R ⁴ and R ⁶ to R ¹² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms constituting the ring. , An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms An aralkyloxy group having 7 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, a hydrocarbylsilyl group having 1 to 20 carbon atoms, or a hetero ring having 3 to 20 carbon atoms constituting the ring Represents a cyclic compound residue. The alkyl group, the cycloalkyl group, the alkenyl group, the aryl group, the alkoxy group, the aralkyloxy group, the aryloxy group, and the hydrocarbylsilyl group in R ¹ to R ¹² have a substituent. It may be. Here, R ¹ and R ³ are different from each other, and R ⁵ and R ⁷ are preferably different from each other. Further, when both R ¹ and R ⁵ are cyclohexyl groups, , R ³ and R ⁷ are preferably not methyl groups.

Among them, R ¹ and R ⁵ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms constituting the ring, or a group having 7 to 30 carbon atoms. An aralkyl group or a hydrocarbylsilyl group having 1 to 20 carbon atoms is preferable, and the alkyl group, the cycloalkyl group, the aralkyl group, the aryl group, and the hydrocarbylsilyl group have a substituent. You may do it. R ³ and R ⁷ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms constituting the ring, or an aryl having 6 to 30 carbon atoms. A hydrocarbylsilyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms constituting the ring, and the number of carbon atoms More preferably, it is an aryl group having 6 to 30 or a hydrocarbylsilyl group having 1 to 20 carbon atoms, and the alkyl group, the cycloalkyl group, the aryl group and the hydrocarbylsilyl group each have a substituent. You may have. On the other hand, R ² , R ⁴ , R ⁶ and R ⁸ to R ¹² are preferably hydrogen atoms.

Further, from the viewpoint that the number of long chain branches (LCB) in the resulting polymer can be increased, R ¹ and R ⁵ constitute an alkyl group or ring having 5 to 10 carbon atoms. Preferably a cycloalkyl group having 3 to 9 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a hydrocarbylsilyl group having 1 to 5 carbon atoms, and having 3 to 9 carbon atoms constituting the ring A cycloalkyl group or an aralkyl group having 10 to 30 carbon atoms is more preferable, and an aralkyl group having 10 to 18 carbon atoms is more preferable.

In addition, in the homopolymerization of ethylene or the copolymerization of ethylene and α-olefin, from the viewpoint that the number of ethyl branches in the resulting polymer can be increased, R ¹ and R ⁵ have 1 to 20 alkyl groups, a cycloalkyl group having 3 to 6 carbon atoms constituting the ring, an aralkyl group having 7 to 30 carbon atoms, or a hydrocarbylsilyl group having 1 to 3 carbon atoms are preferable. More preferred are ˜30 aralkyl groups.

Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group. N-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, n-hexyl group, texyl group, neohexyl group, n-heptyl group, n-octyl group, n-decyl group, n-dodecyl group, n- Pentadecyl group, n-eicosyl group, perfluoromethyl group, perfluoroethyl group, perfluoro-n-propyl group, perfluoroisopropyl group, perfluoro-n-butyl group, perfluoro-sec-butyl group, perfluoroisobutyl Group, perfluoro-tert-butyl group, perfluoro-n-pentyl group, perfluoroiso Nyl group, perfluoro-tert-pentyl group, perfluoronepentyl group, perfluoro-n-hexyl group, perfluoro-n-heptyl group, perfluoro-n-octyl group, perfluoro-n-decyl group, perfluoro Examples include a fluoro-n-dodecyl group, a perfluoro-n-pentadecyl group, and a perfluoro-n-eicosyl group. In R ¹ and R ⁵ , from the viewpoint that the molecular weight of the resulting polymer can be improved, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, Alkyl groups having 4 to 10 carbon atoms such as tert-pentyl group, neopentyl group, n-hexyl group, texyl group, neohexyl group, n-heptyl group, n-octyl group and n-decyl group are preferred, and n-butyl More preferred are alkyl groups having 4 to 8 carbon atoms such as a group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group and texyl group. Of these, tertiary alkyl groups having 4 to 8 carbon atoms such as tert-butyl group, tert-pentyl group, and texyl group are particularly preferable, and the molecular weight of the resulting polymer can be improved. From the viewpoint that it can be increased, a tertiary alkyl group having 5 to 8 carbon atoms such as a tert-pentyl group or a texyl group is most preferable. On the other hand, in R ² to R ⁴ and R ⁶ to R ⁸ , perfluoromethyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert- 4 carbon atoms such as butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, texyl, neohexyl, n-heptyl, n-octyl, n-decyl Is preferably an alkyl group having 1 to 8 carbon atoms, such as a perfluoromethyl group, a methyl group, an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, or a texyl group. More preferably a perfluoromethyl group, a methyl group, an isopropyl group, an isobutyl group, a tert-butyl group. An alkyl group having 1 to 4 carbon atoms more preferred such groups.

Examples of the cycloalkyl group having 3 to 10 carbon atoms constituting the substituted or unsubstituted ring include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and 1-methylcyclopentyl. Group, 1-methylcyclohexyl group, 1-phenylcyclohexyl group, 1-indanyl group, 2-indanyl group, norbornyl group, bornyl group, menthyl group, 1-adamantyl group, 2-adamantyl group, 3,5-dimethyladamantyl group 3,5,7-trimethyladamantyl group, 3,5-diethyladamantyl group, 3,5,7-triethyladamantyl group, 3,5-diisopropyladamantyl group, 3,5,7-triisopropyladamantyl group, 3, 5-diisobutyladamantyl group, 3,5,7- Lysobutyladamantyl group, 3,5-diphenyladamantyl group, 3,5,7-triphenyladamantyl group, 3,5-di (p-toluyl) adamantyl group, 3,5,7-tri (p-toluyl) adamantyl group Group, a 3,5-di (3,5-xylyl) adamantyl group, a 3,5,7-tri (3,5-xylyl) adamantyl group, and the like. From the viewpoint that the molecular weight of the resulting polymer can be improved, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, 1-methylcyclopentyl group, 1-methylcyclohexyl group, 1-indanyl group, 2-indanyl Group, norbornyl group, bornyl group, menthyl group, 1-adamantyl group, 2-adamantyl group, 3,5-dimethyladamantyl group, 3,5-diethyladamantyl group, 3,5-diphenyladamantyl group, 3,5-di (P-toluyl) adamantyl group and 3,5-di (3,5-xylyl) adamantyl group, etc., cycloalkyl groups having 5 to 26 carbon atoms (including carbon atoms other than the carbon atoms constituting the ring) Preferred is a cyclohexyl group, 1-methylcyclohexyl group, norbornyl group, bornyl group 6 to 14 carbon atoms such as 1-adamantyl group, 2-adamantyl group, 3,5-dimethyladamantyl group and 3,5-diethyladamantyl group (including carbon atoms other than the carbon atoms constituting the ring) A cycloalkyl group is more preferred. From the viewpoint of improving the molecular weight of the resulting polymer and increasing the LCB, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a 1-methylcyclopentyl group, a 1-methylcyclohexyl group. A cycloalkyl group having 3 to 9 carbon atoms (including carbon atoms other than carbon atoms constituting the ring) such as a group, 1-indanyl group, 2-indanyl group, norbornyl group, menthyl group, etc., is preferably a cyclopentyl group Cycloalkyl having 3 to 7 carbon atoms (including carbon atoms other than carbon atoms constituting the ring) such as cyclohexyl group, cycloheptyl group, cyclooctyl group, 1-methylcyclopentyl group, 1-methylcyclohexyl group, etc. Groups are more preferred.

Examples of the substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms include vinyl group, allyl group, propenyl group, 2-methyl-2-propenyl group, homoallyl group, pentenyl group, hexenyl group, heptenyl group, octenyl Group, nonenyl group, decenyl group and the like. From the viewpoint that the molecular weight of the resulting polymer can be improved, an alkenyl group having 3 to 6 carbon atoms is preferable, and an allyl group and a homoallyl group are more preferable.

Examples of the substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 3-methyl-1-butynyl group, 3,3-dimethyl group. -1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 4-methyl-1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 4-methyl-1 -Pentenyl group, 1-hexynyl group, 1-octynyl group, phenylethynyl group and the like. From the viewpoint of improving the molecular weight of the resulting polymer, an alkynyl group having 3 to 8 carbon atoms is preferable, and a 3-methyl-1-butynyl group, a 3,3-dimethyl-1-butynyl group, 4 More preferred are a methyl-1-pentenyl group and a phenylethynyl group.

Examples of the substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, ( 2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) ) Methyl group, (3,5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) ) Methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) Til group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (N-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (isobutylphenyl) methyl group, (N-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, naphthylmethyl group, anthracene Nylmethyl group, dimethyl (phenyl) methyl group, dimethyl (4-methylphenyl) methyl group, dimethyl 1-naphthyl) methyl group, dimethyl (2-naphthyl) methyl group, methyl (ethyl) (phenyl) methyl group, methyl (diphenyl) methyl group, methylbis (4-methylphenyl) methyl group, dimethyl (3,5-dimethyl) A phenyl) methyl group, a dimethyl (4-dibenzofuranyl) methyl group, a diethyl (phenyl) methyl group, and a triphenylmethyl group. From the viewpoint that the molecular weight of the resulting polymer can be improved and LCB can be increased, benzyl group, naphthylmethyl group, anthracenylmethyl group, dimethyl (phenyl) methyl group, dimethyl (4- Methylphenyl) methyl group, dimethyl (1-naphthyl) methyl group, dimethyl (2-naphthyl) methyl group, methyl (ethyl) (phenyl) methyl group, methyl (diphenyl) methyl group, methylbis (4-methylphenyl) methyl group Dimethyl (3,5-dimethylphenyl) methyl group, dimethyl (4-dibenzofuranyl) methyl group, diethyl (phenyl) methyl group and triphenylmethyl group are preferred, dimethyl (phenyl) methyl group, dimethyl (4-methyl Phenyl) methyl group, dimethyl (1-naphthyl) methyl group, dimethyl 2-naphthyl) methyl group, methyl (ethyl) (phenyl) methyl group, methyl (diphenyl) methyl group, methylbis (4-methylphenyl) methyl group, dimethyl (3,5-dimethylphenyl) methyl group, dimethyl (4- Tertiary aralkyl groups having 9 to 20 carbon atoms such as dibenzofuranyl) methyl group, diethyl (phenyl) methyl group and triphenylmethyl group are more preferred, such as benzyl group, naphthylmethyl group, anthracenylmethyl group, dimethyl group (Phenyl) methyl group, dimethyl (4-methylphenyl) methyl group, dimethyl (1-naphthyl) methyl group, dimethyl (2-naphthyl) methyl group, methyl (ethyl) (phenyl) methyl group, methyl (diphenyl) methyl group Methylbis (4-methylphenyl) methyl group, dimethyl (3,5-dimethyl) Phenyl) methyl group, dimethyl (4-dibenzofuranyl) methyl group, diethyl (phenyl) methyl group and triphenylmethyl group are preferred, dimethyl (phenyl) methyl group, dimethyl (4-methylphenyl) methyl group, dimethyl (1 -Naphthyl) methyl group, dimethyl (2-naphthyl) methyl group, methyl (ethyl) (phenyl) methyl group, methyl (diphenyl) methyl group, dimethyl (3,5-dimethylphenyl) methyl group, dimethyl (4-dibenzofura) More preferred are tertiary aralkyl groups having 9 to 18 carbon atoms, such as a dimethyl (phenyl) methyl group, a dimethyl (4-methylphenyl) methyl group and a dimethyl (4-methylphenyl) methyl group. Methylphenyl) methyl group, dimethyl (1-naphthyl) methyl group, dimethyl Ru (2-naphthyl) methyl group, methyl (ethyl) (phenyl) methyl group, methyl (diphenyl) methyl group, dimethyl (3,5-dimethylphenyl) methyl group, diethyl (phenyl) methyl group and methylbis (4-methyl) Most preferred is a tertiary aralkyl group having 9 to 18 carbon atoms consisting of only a carbon atom such as a phenyl) methyl group and a hydrogen atom. From the viewpoint that the molecular weight of the resulting polymer can be improved and the number of ethyl branches in the resulting polymer can be increased in the homopolymerization of ethylene, a benzyl group, a naphthylmethyl group, an anthracenylmethyl group Dimethyl (phenyl) methyl group, dimethyl (4-methylphenyl) methyl group, dimethyl (1-naphthyl) methyl group, dimethyl (2-naphthyl) methyl group, methyl (ethyl) (phenyl) methyl group, methyl (diphenyl) A methyl group, a dimethyl (3,5-dimethylphenyl) methyl group, a dimethyl (4-dibenzofuranyl) methyl group, a diethyl (phenyl) methyl group, a methylbis (4-methylphenyl) methyl group, and a triphenylmethyl group are preferable. Dimethyl (phenyl) methyl group, dimethyl (4-methylpheny ) Methyl group, dimethyl (1-naphthyl) methyl group, dimethyl (2-naphthyl) methyl group, methyl (ethyl) (phenyl) methyl group, methyl (diphenyl) methyl group, methylbis (4-methylphenyl) methyl group, dimethyl Tertiary aralkyl groups having 9 to 20 carbon atoms such as (3,5-dimethylphenyl) methyl group, dimethyl (4-dibenzofuranyl) methyl group, diethyl (phenyl) methyl group and triphenylmethyl group are more preferable. Dimethyl (phenyl) methyl group, dimethyl (4-methylphenyl) methyl group, dimethyl (1-naphthyl) methyl group, dimethyl (2-naphthyl) methyl group, methyl (ethyl) (phenyl) methyl group, methyl (diphenyl) Methyl group, dimethyl (3,5-dimethylphenyl) methyl group, dimethyl (4-diben) Furanyl) methyl group, a tertiary aralkyl group having a carbon number of 9-18 such as diethyl (phenyl) methyl and methyl bis (4-methylphenyl) methyl group is more preferable.

Examples of the substituted or unsubstituted aryl group having 6 to 30 carbon atoms in R ² to R ⁴ and R ⁶ to R ¹² include a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, 2 , 3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetra Methylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n - Ruphenyl group, sec-butylphenyl group, tert-butylphenyl group, isobutylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n- Dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, anthracenyl group, 3,5-diisopropylphenyl group, 2,6-diisopropylphenyl group, 3,5-ditert-butylphenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, pentafluorophenyl group, 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 2,3-difluorophenyl group, 2 , 4-difluorophenyl group, 2,5- Fluorophenyl group, 2,6-difluorophenyl group, 2-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, A 4-bromophenyl group, a 2,3-dibromophenyl group, a 2,4-dibromophenyl group, or a 2,5-dibromophenyl group, preferably a phenyl group, a 2-tolyl group, a 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3 , 4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethyl 6 to 6 carbon atoms such as ruphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, 3,5-diisopropylphenyl group, 2,6-diisopropylphenyl group, 3,5-ditert-butylphenyl group 20 phenyl groups; 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, pentafluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl Fluorinated phenyl groups such as 2,6-difluorophenyl groups; fluorinated alkylphenyl groups such as 2-trifluoromethylphenyl groups, 3-trifluoromethylphenyl groups, 4-trifluoromethylphenyl groups, and more Preferably, phenyl group, 2-tolyl group, 3-tolyl group, 4-toluene Group, 2,6-xylyl group, 3,5-xylyl group, 2,4,6-trimethylphenyl group, 3,5-diisopropylphenyl group, 2,6-diisopropylphenyl group, 3,5-ditert- Butylphenyl group, 2-fluorophenyl group, pentafluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, 2,4 , 6-trifluorophenyl group.

Examples of the substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms include a perfluoromethoxy group, a perfluoroethoxy group, a perfluoro-n-propoxy group, a perfluoroisopropoxy group, and a perfluoro-n-butoxy group. Perfluoro-sec-butoxy group, perfluoroisobutoxy group, perfluoro-n-pentyloxy group, perfluoronepentyloxy group, perfluoro-n-hexyloxy group, perfluoro-n-heptyloxy group, perfluoro Fluoro-n-octyloxy group, perfluoro-n-decyloxy group, perfluoro-n-dodecyloxy group, perfluoro-n-pentadecyloxy group, perfluoro-n-eicosyloxy group, methoxy group, ethoxy group , N-propoxy group, isopropoxy group, n-but Si group, sec-butoxy group, isobutoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-decyloxy group, n-dodecyloxy group N-pentadecyloxy group and n-eicosyloxy group. From the viewpoint of improving the molecular weight of the resulting polymer, an alkoxy group having 1 to 4 carbon atoms is preferable, and a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and an n-butoxy group are more preferable. preferable.

Examples of the substituted or unsubstituted aralkyloxy group having 7 to 30 carbon atoms include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, and (4-methylphenyl) methoxy group. , (2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4- (Dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6- Trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, 3,4,5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group, (2,3,5 , 6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (Sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, (n-tetradecyl) Phenyl) methoxy group, naphthylmethoxy group, anthracenylmethoxy group and the like. From the viewpoint of improving the molecular weight of the resulting polymer, an aralkyloxy group having 7 to 12 carbon atoms is preferable, and a benzyloxy group is more preferable.

Examples of the substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms include phenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy. 2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2, 3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, 2,6-diisopropylphenoxy group, 2-fluorophenoxy group, 3-fluorophenoxy group, 4-fluorophenoxy group, pentafluorophenoxy group, 2-triphenyl Fluoromethylphenoxy group, 3-trifluoromethylphenoxy group, 4-trifluoromethylphenoxy group 2,3-difluorophenoxy group, 2,4-fluorophenoxy group, 2,5-difluorophenoxy group, 2-chlorophenoxy group, 2,3-dichlorophenoxy group, 2,4-dichlorophenoxy group, 2,5- Examples include dichlorophenoxy group, 2-bromophenoxy group, 3-bromophenoxy group, 4-bromophenoxy group, 2,3-dibromophenoxy group, 2,4-dibromophenoxy group, and 2,5-dibromophenoxy group. From the viewpoint that the molecular weight of the resulting polymer can be improved, aryloxy groups having 6 to 14 carbon atoms are preferred, and 2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group, More preferred are 2,6-diisopropylphenoxy group and pentafluorophenoxy group.

Examples of the substituted or unsubstituted hydrocarbylsilyl group having 1 to 20 carbon atoms include trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, Isobutylsilyl group, tert-butyldimethylsilyl group, methyldiphenylsilyl group, dimethyl (phenyl) silyl group, tert-butyldiphenylsilyl group, triphenylsilyl group, methylbis (trimethylsilyl) silyl group, dimethyl (trimethylsilyl) silyl group and tris (Trimethylsilyl) silyl group and the like can be mentioned. From the viewpoint that the molecular weight of the resulting polymer can be improved and LCB can be increased, trialkylsilyl having 3 to 5 carbon atoms such as trimethylsilyl group, ethyldimethylsilyl group, diethylmethylsilyl group, etc. And a silyl group having a hydrocarbylsilyl group having 3 to 20 carbon atoms as a substituent, such as methylbis (trimethylsilyl) silyl group, dimethyl (trimethylsilyl) silyl group and tris (trimethylsilyl) silyl group, is preferred. Is more preferable.

Examples of the substituted or unsubstituted heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring include thienyl group, furyl group, 1-pyrrolyl group, 1-imidazolyl group, 1-pyrazolyl group, pyridyl group. Group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, 2-isoindolyl group, 1-indolyl group, quinolyl group, dibenzo-1H-pyrrol-1-yl group and the like, preferably thienyl group, furyl group, 1- A pyrrolyl group, a pyridyl group, a pyrimidinyl group, a 2-isoindolyl group, a 1-indolyl group, a quinolyl group, and a dibenzo-1H-pyrrol-1-yl group.

R ¹ and R ² may be linked to each other to form a ring. Similarly, R ² and R ³ may be connected to each other to form a ring. Similarly, R ³ and R ⁴ may be connected to each other to form a ring. Similarly, R ⁵ and R ⁶ may be linked to each other to form a ring. Similarly, R ⁶ and R ⁷ may be linked to each other to form a ring. Similarly, R ⁷ and R ⁸ may be linked to each other to form a ring. When linked to each other to form a ring, it is preferably a 4- to 10-membered hydrocarbyl ring or heterocyclic ring containing two carbon atoms on the benzene ring, and the ring may have a substituent. Good.

As described above, the ring formed by connecting two adjacent R ¹ to R ⁸ specifically includes a cyclobutene ring, a cyclopentene ring, a cyclopentadiene ring, a cyclohexene ring, a cycloheptene ring, a cyclooctene ring, Benzene ring, naphthalene ring, furan ring, 2,5-dimethylfuran ring, thiophene ring, 2,5-dimethylthiophene ring and pyridine ring are preferable, and cyclobutene ring, cyclopentene ring, cyclopentadiene ring, cyclohexene ring are preferable. , A benzene ring and a naphthalene ring, more preferably a cyclopentene ring, a cyclopentadiene ring, a cyclohexene ring, a benzene ring and a naphthalene ring formed by linking R ¹ and R ² , and R ⁵ and R ⁶ .

Regardless of the definitions of R ⁹ to R ¹² above, R ⁹ and R ¹⁰ , and R ¹¹ and R ¹² may be independently connected to each other to form a ring, and the ring has a substituent. You may do it.

An alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, a carbon atom in L An aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkyloxy group having 7 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, and a hydrocarbyl having 1 to 20 carbon atoms The silyl group is the same as these groups in R ² to R ⁴ and R ⁶ to R ¹² .

Examples of the substituted or unsubstituted hydrocarbylamino group having 1 to 20 carbon atoms in L include, for example, a dimethylamino group, a diethylamino group, a di-n-butylamino group, a di-n-propylamino group, a diisopropylamino group, a diisopropyl group, A benzylamino group, a diphenylamino group and the like, preferably a hydrocarbylamino group having 2 to 14 carbon atoms, more preferably a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group And a dibenzylamino group.

Examples of the substituted or unsubstituted hydrocarbylthiolate group having 1 to 20 carbon atoms in L include, for example, a thiophenoxy group, a 2,3,4-trimethylthiophenoxy group, a 2,3,5-trimethylthiophenoxy group, 2,3,6-trimethylthiophenoxy group, 2,4,6-trimethylthiophenoxy group, 3,4,5-trimethylthiophenoxy group, 2,3,4,5-tetramethylthiophenoxy group, 4,6-tetramethylthiophenoxy group, 2,3,5,6-tetramethylthiophenoxy group, pentamethylthiophenoxy group, 2-fluorothiophenoxy group, 3-fluorothiophenoxy group, 4-fluorothiophenoxy group, pentafluoro Thiophenoxy group, 2-trifluoromethylthiophenoxy group, 3-trifluoromethyl Ofenoxy group, 4-trifluoromethylthiophenoxy group, 2,3-difluorothiophenoxy group, 2,4-fluorothiophenoxy group, 2,5-difluorothiophenoxy group, 2-chlorothiophenoxy group, 2,3-dichloro Thiophenoxy group, 2,4-dichlorothiophenoxy group, 2,5-dichlorothiophenoxy group, 2-bromothiophenoxy group, 3-bromothiophenoxy group, 4-bromothiophenoxy group, 2,3-dibromothiophenoxy group Group, 2,4-dibromothiophenoxy group, 2,5-dibromothiophenoxy group and the like, preferably a hydrocarbylthiolate group having 6 to 12 carbon atoms, more preferably a thiophenoxy group, 4,6-trimethylthiophenoxy group, 3,4,5-trimethylthiopheno Si group, 2,3,4,5-tetramethylthiophenoxy group, 2,3,4,6-tetramethylthiophenoxy group, 2,3,5,6-tetramethylthiophenoxy group, pentamethylthiophenoxy group and pentafluorothio It is a phenoxy group.

Examples of the substituted or unsubstituted carboxylate group having 1 to 20 carbon atoms in L include an acetate group, a propionate group, a butyrate group, a pentanate group, a hexanoate group, a 2-ethylhexanoate group, and a trifluoroacetate group. Preferred is a carboxylate group having 2 to 10 carbon atoms, and more preferred are an acetate group, a propionate group, a 2-ethylhexanoate group, and a trifluoroacetate group.

L is preferably a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, an amino group, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. Groups, aryloxy groups having 6 to 30 carbon atoms, hydrocarbylsilyl groups having 1 to 20 carbon atoms, and hydrocarbylamino groups having 1 to 20 carbon atoms. More preferably, a chlorine atom, a bromine atom, an alkyl group having 1 to 6 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms And a hydrocarbylamino group having 2 to 10 carbon atoms, more preferably a chlorine atom, a methyl group, an ethyl group, an n-butyl group, a tert-butyl group, a benzyl group, a methoxy group, an ethoxy group, an isopropoxy group Group, tert-butoxy group, phenoxy group, dimethylamino group and diethylamino group, particularly preferably a chlorine atom, methyl group, benzyl group, isopropoxy group, phenoxy group and dimethylamino group, most preferably chlorine Atomic and benzyl groups.

Specific examples of the complex represented by the general formula (1) include, for example, the following compounds.

In addition to these, for example, a benzyl group directly bonded to the hafnium atom of these compounds may be a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a dimethylamino group, a diethylamino group, a methoxy group, an ethoxy group. Or a compound changed to a t-butoxy group.

Furthermore, the compound which changed the group corresponded to R < ³ > and R < ⁷ > of said each compound into the hydrogen atom or the methyl group can also be mentioned, for example.

Furthermore, for example, compounds in which the 8-membered ring portion bridging between the sulfur atoms of each of the above compounds is changed to a 7-membered ring can also be mentioned.

Examples thereof also include compounds in which the groups corresponding to R ⁹ to R ¹² in each of the above compounds are substituted with a methyl group or an ethyl group.

Preferred examples of complex (1) include the following compounds.

Also, compounds in which the benzyl group directly bonded to the hafnium atom of these compounds is changed to a chlorine atom can be mentioned.

There can also be mentioned compounds in which the groups corresponding to R ³ and R ⁷ in each of the above compounds are changed to methyl groups.

The complex represented by the general formula (1) includes a compound represented by the following general formula (2) (hereinafter referred to as compound (2)) and a compound represented by the following general formula (3) (hereinafter referred to as compound). (Referred to as (3)) as a starting material, but can be produced by the following reaction scheme 1, but is not limited to this method.

Compound (2) n and ^R 1 ^{~ R 12} being are respectively similar to n and ^R 1 ^{~ R 12} in the general formula (1).

L in the compound (3) is the same as L in the general formula (1). Compound (3) may, for _{_{example, Hf (CH 2 Ph) 4}} , HfCl 2 (CH 2 Ph) 2, Hf (CH 2 SiMe 3) 4, HfF 4, HfCl 4, HfBr 4, HfI 4, Hf (OMe) ₄ , Hf (OEt) ₄ , Hf (Oi-Pr) ₄ , HfCl ₂ (Oi-Pr) ₂ , Hf (On-Bu) ₄ , Hf (Oi-Bu) ₄ , Hf (O -T-Bu) ₄ , Hf (NMe ₂ ) ₄ , HfCl ₂ (NMe ₂ ) _2, Hf (NEt ₂ ) _{4 and the} like. _{_{Preferably, Hf (CH 2 Ph) 4}} , HfCl 2 (CH 2 Ph) 2, Hf (CH 2 SiMe 3) 4, HfCl 4, HfBr 4, Hf (OMe) 4, Hf (OEt) 4, Hf (Oi -Pr) ₄ , Hf (Oi-Bu) ₄ , Hf (Ot-Bu) ₄ , Hf (NMe ₂ ) ₄ , HfCl ₂ (NMe ₂ ) ₂ , Hf (NEt ₂ ) ₄ .

In the above reaction scheme 1, the compound (2) and the compound (3) may be reacted as they are in a solvent, and the compound (3) is reacted after reacting the compound (2) with a base as necessary. You may let them. As a base made to react with a compound (2), an organolithium reagent, a Grignard reagent, and a metal hydride are mentioned, for example. Specific examples include methyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, lithium diisopropylamide, lithium hexamethyldisilazane, potassium hexamethyldisilazane, sodium hydride and potassium hydride. it can. Of these, n-butyllithium, lithium diisopropylamide, potassium hexamethyldisilazane, sodium hydride and potassium hydride are preferable.

The compound obtained by reacting the hafnium complex represented by the general formula (1), the compound (3), and the compound (2) with a base is unstable with respect to air and moisture. Therefore, the reaction in Reaction Scheme 1 is preferably performed under dehydration and deoxygenation. Specifically, it is under dry helium, dry argon or dry nitrogen, more preferably under dry argon or dry nitrogen.

In the above reaction scheme 1, the amount of the compound (2) used may be 1 molar equivalent or more with respect to the compound (3), preferably in the range of 1.0 to 1.5. Moreover, when the compound (2) remains in the course of the reaction, the compound (3) may be added during the reaction.

The temperature at which the compound (2) and the compound (3) are reacted is preferably in the temperature range of −100 ° C. to 150 ° C., more preferably in the temperature range of −80 ° C. to 50 ° C. However, it is not intended to be limited to this range.

The reaction between the compound (2) and the compound (3) may be carried out until the time when the yield of the product becomes the highest, preferably 5 minutes to 48 hours, more preferably 10 minutes to 24 hours, More preferably, it is 30 minutes to 18 hours.

When the compound (2) and the base are reacted, the temperature at which the compound (2) and the base are reacted is preferably in the temperature range of −100 ° C. to 150 ° C., more preferably −80 ° C. to 50 ° C. Temperature range. However, it is not intended to be limited to this range.

Further, the reaction time of the compound (2) and the base may be carried out until the product yield becomes the highest, preferably 5 minutes to 24 hours, more preferably 10 minutes to 12 hours, Preferably, it is 30 minutes to 3 hours.

When the compound (2) is reacted with the base, the temperature at which the compound (3) is reacted with the compound formed by reacting the compound (2) with the base is preferably −100 ° C. to 150 ° C. The temperature range is more preferably -80 ° C to 50 ° C. However, it is not intended to be limited to this range.

In addition, the reaction time between the compound (2) and the compound produced by reacting the base with the compound (3) may be the time until the yield of the product becomes the highest, and preferably 5 minutes to 48 minutes. The time is more preferably 10 minutes to 24 hours, and further preferably 30 minutes to 3 hours.

The solvent used in the reaction shown in Reaction Scheme 1 is not particularly limited as long as it is a solvent generally used in similar reactions, and includes a hydrocarbon solvent and an ether solvent. Preferred are toluene, benzene, o-xylene, m-xylene, p-xylene, hexane, pentane, heptane, cyclohexane, diethyl ether and tetrahydrofuran, and more preferred are diethyl ether, toluene, tetrahydrofuran, hexane, pentane and heptane. And cyclohexane.

Compound (2) can be synthesized, for example, according to the method described in Non-Patent Document 8.
Specifically, it can be produced by the following reaction scheme 2. However, the preparation method of the compound (2) should not be limited to this method. Hereinafter, each step in Reaction Scheme 2 will be described.

N and R ¹ to R ¹² contained in at least one of the compounds represented by the general formulas (4) to (7) (hereinafter referred to as the compounds (4) to (7), respectively) The same as n and R ¹ to R ¹² in the formula (1).

X ′ in compound (5) and compound (7) represents an anionic leaving group, for example, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, acetate group, trifluoroacetate group, benzoate group, CF ₃ SO ₃ group, CH ₃ SO ₃ group, 4-MeC ₆ H ₄ SO ₃ group or PhSO ₃ group, etc., preferably chlorine atom, bromine atom, iodine atom, CF ₃ SO ₃ group, CH ₃ SO ₃ A 4-MeC ₆ H ₄ SO ₃ group or a PhSO ₃ group.

[Step 1]
trans-cycloheptane-1,2-dithiol (compound (4) when n = 2) or trans-cyclooctane-1,2-dithiol (compound (4) when n = 3) Compound (6) can be synthesized by reacting 0 to 4.0 molar equivalents, preferably 1.0 to 1.5 molar equivalents, of compound (5) in the presence of a base.

The base is not particularly limited, but includes inorganic bases such as potassium carbonate, calcium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and calcium carbonate, and amine bases such as triethylamine and triisobutylamine. An amine base is preferred.

This reaction can be performed in an atmosphere of air, helium, argon, or nitrogen. Preferably, it is under a helium, argon or nitrogen atmosphere, more preferably under a nitrogen or argon atmosphere.

After completion of the reaction, the compound (6) may be purified as necessary. Examples of the purification method include a method of adding an aqueous ammonium chloride solution, an aqueous hydrochloric acid solution or an aqueous sodium chloride solution to the reaction solution, then adding ethyl acetate or diethyl ether, and performing an extraction operation to remove excess base or salt. It is done. Further, the purity can be increased by purification operations such as distillation, recrystallization and silica gel chromatography.

[Step 2]
Compound (2) can be synthesized by reacting compound (6) with 1.0 to 4.0 molar equivalents, preferably 1.0 to 1.5 molar equivalents of compound (7) in the presence of a base.

After completion of the reaction, the compound (2) may be purified as necessary. Examples of the purification method include a method of adding an aqueous ammonium chloride solution, an aqueous hydrochloric acid solution or an aqueous sodium chloride solution to the reaction solution, then adding ethyl acetate or diethyl ether, and performing an extraction operation to remove excess base or salt. It is done. Further, the purity can be increased by purification operations such as distillation, recrystallization and silica gel chromatography.

The compound (2) can also be obtained by reacting the compound (6) and the compound (7) produced in the reactor by controlling the reaction conditions of [step 1].

R ¹ and R ⁵ are the same group, R ² and R ⁶ are the same group, R ³ and R ⁷ are the same group, R ⁴ is the same group as R ⁸ , and When the combination of the groups R ⁹ and R ¹⁰ is the same as the combination of the groups R ¹¹ and R ¹² , the compound (5) and the compound (7) are combined to form the compound (4). Compound (2) can also be synthesized by reacting 2.0 to 8.0 molar equivalents, preferably 2.0 to 4.0 molar equivalents in the presence of a base.

Specific examples of the compound (2) include the following compounds.

In addition, for example, compounds in which groups corresponding to R ³ and R ⁷ of these compounds are substituted with a hydrogen atom or a methyl group can also be mentioned.

Furthermore, for example, compounds in which the 8-membered ring part that bridges between the sulfur atoms in each of the above compounds is changed to a 7-membered ring can also be mentioned.

Furthermore, for example, compounds in which the groups corresponding to R ⁹ to R ¹² in each of the above compounds are substituted with a methyl group or an ethyl group can also be mentioned.

Specific examples of the compound (5) and the compound (7) include the following compounds.

In addition, for example, compounds in which a group corresponding to R ³ or R ⁷ of these compounds is substituted with a hydrogen atom or a methyl group can also be mentioned.

The complex represented by the general formula (1) described above is used as a polymerization catalyst component when a polymer is produced by homopolymerization of ethylene or copolymerization of ethylene and α-olefin. Preferably, it is used as a catalyst component for homopolymerization.

As the polymerization catalyst, it is preferable to use a polymerization catalyst obtained by contacting the complex represented by the general formula (1) and the promoter component (A). Examples of the promoter component (A) include an activation promoter component containing a Group 13 element in the periodic table, for example,
It preferably contains at least one compound selected from the group consisting of (A-1) an organoaluminum compound and (A-2) a boron compound.

[Organic aluminum compound (A-1)]
As the organoaluminum compound (A-1) used in the present invention, a known organoaluminum compound can be used. For example, (A-1-1) an organoaluminum represented by the general formula E ¹ _a AlY ¹ _3-a A compound, (A-1-2) a cyclic aluminoxane having a structure represented by the general formula {-Al (E ² ) —O—} _b , and (A-1-3) a general formula E ³ {-Al ( A linear aluminoxane having a structure represented by E ³ ) —O—} _c AlE ³ ₂ (where E ¹ , E ² , and E ³ are hydrocarbyl groups having 1 to 8 carbon atoms; All E ¹ , all E ² and all E ³ may be the same or different Y ¹ represents a hydrogen atom or a halogen atom, and all Y ¹ are the same or different A is 1, 2 or 3, b is 2 An integer of above, c is can be exemplified one or a mixture of two or three kinds of them among the representative.) An integer of 1 or more.

Specific examples of the organoaluminum compound (A-1-1) represented by the general formula E ¹ _a AlY ¹ _3-a include trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trihexylaluminum. Dialkylaluminum chlorides such as dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride and dihexylaluminum chloride; methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride and hexylaluminum dichloride Alkyl aluminum dichlori ; And it can be exemplified dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, dialkyl aluminum hydride such as diisobutylaluminum hydride and dihexyl aluminum hydride. Trialkylaluminum is preferable, and triethylaluminum and triisobutylaluminum are more preferable.

Formula ^{_{{-Al (E 2) -O-}}} E 2 in the aluminoxane (A-1-2) of the annular having a structure represented by _b, and the general formula ^{^{E 3 {-Al (E 3)}} -O- } _C Specific examples of E ^{3 in} the linear aluminoxane (A-1-3) having a structure represented by AlE ³ ₂ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. And alkyl groups such as isobutyl group, n-pentyl group and neopentyl group. Of these, a methyl group and an isobutyl group are preferable.

B in the general formula {—Al (E ² ) —O—} _b is an integer of 2 or more, and _{c in} the general formula E ³ {—Al (E ³ ) —O—} _c AlE ³ ₂ is an integer of 1 or more. It is. Among these, b is preferably 2 or more and 40 or less, and c is preferably 1 or more and 40 or less.

The above aluminoxane can be made by various methods. There is no restriction | limiting in particular about the method, What is necessary is just to make according to a well-known method. For example, a method in which a solution obtained by dissolving a trialkylaluminum (such as trimethylaluminum) in an appropriate organic solvent (such as benzene, toluene, and aliphatic hydrocarbon) is brought into contact with water to form an aluminoxane. Or the method of making aluminoxane by making trialkylaluminum (for example, trimethylaluminum etc.) contact the metal salt (for example, copper sulfate hydrate etc.) containing crystal water is mentioned.

In addition, a cyclic aluminoxane (A-1-2) having a structure represented by the general formula {-Al (E ² ) —O—} _b obtained by the above method, and a general formula E ³ {-Al ( The linear aluminoxane (A-1-3) having a structure represented by E ³ ) —O—} _c AlE ³ ₂ may be used after removing volatile components by distillation, if necessary. . Further, the compound obtained by distilling off the volatile components and drying may be washed with an appropriate organic solvent (benzene, toluene, aliphatic hydrocarbon, etc.), and dried again for use.

[Boron compound (A-2)]
As the boron compound (A-2) used in the present invention, (A-2-1) a boron compound represented by the general formula BR ¹³ R ¹⁴ R ¹⁵ , (A-2-2) a general formula W ⁺ (BR ¹³ R ¹⁴ R ¹⁵ R ¹⁶ ) ^— and a boron compound represented by (A-2-3) general formula (VH) ⁺ (BR ¹³ R ¹⁴ R ¹⁵ R ¹⁶ ) ^— Either can be used suitably.

In the boron compound (A-2-1) represented by the general formula BR ¹³ R ¹⁴ R ¹⁵ , B is a boron atom in a trivalent valence state, R ¹³ to R ¹⁵ are halogen atoms, and the number of carbon atoms is 1. A hydrocarbyl group having ˜20, a halogenated hydrocarbyl group having 1 to 20 carbon atoms, a substituted silyl group containing 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 2 to 20 carbon atoms A disubstituted amino group containing carbon atoms, which may be the same or different; Preferred R ¹³ to R ¹⁵ are a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, and a halogenated hydrocarbyl group having 1 to 20 carbon atoms.

Specific examples of the boron compound (A-2-1) include triphenylborane, tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,4). , 5-tetrafluorophenyl) borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, and phenylbis (pentafluorophenyl) borane. . Of these, triphenylborane and tris (pentafluorophenyl) borane are preferable.

In the boron compound (A-2-2) represented by the general formula W ⁺ (BR ¹³ R ¹⁴ R ¹⁵ R ¹⁶ ) ⁻ , W ⁺ is an inorganic or organic cation, and B is a trivalent valence state. It is a boron atom, and R ¹³ to R ¹⁶ are the same as R ¹³ to R ¹⁵ in the boron compound (A-2-1).
That is, R ¹³ to R ¹⁶ are a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, a halogenated hydrocarbyl group having 1 to 20 carbon atoms, a substituted silyl group containing 1 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms or a disubstituted amino group containing 2 to 20 carbon atoms, which may be the same or different; R ⁹ to R ¹² are preferably a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, or a halogenated hydrocarbyl group having 1 to 20 carbon atoms.

Examples of W ⁺ that is an inorganic cation include a ferrocenium cation, an alkyl-substituted ferrocenium cation, and a silver cation. Examples of W ⁺ that is an organic cation include a triphenylcarbenium cation. (BR ¹³ R ¹⁴ R ¹⁵ R ¹⁶ ) ^— includes tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluoro). Phenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,3,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate, and tetrakis [3,5- And bis (trifluoromethyl) phenyl] borate.

Specific examples of the boron compound (A-2-2) represented by the general formula W ⁺ (BR ¹³ R ¹⁴ R ¹⁵ R ¹⁶ ) ^— include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′- Dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, and triphenylcarbeniumtetrakis [3,5-bis (trifluoromethyl) Phenyl] borate and the like. Of these, triphenylcarbenium tetrakis (pentafluorophenyl) borate is particularly preferable.

In the boron compound (A-2-3) represented by the general formula (VH) ⁺ (BR ¹³ R ¹⁴ R ¹⁵ R ¹⁶ ) ⁻ , V is a neutral Lewis base, and (VH) ⁺ Is a Bronsted acid, B is a boron atom in a trivalent valence state, and R ¹³ to R ¹⁶ are the same as R ¹³ to R ¹⁵ in the boron compound (A-2-1). That is, R ¹³ to R ¹⁶ are a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, a halogenated hydrocarbyl group having 1 to 20 carbon atoms, a substituted silyl group containing 1 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms or a disubstituted amino group containing 2 to 20 carbon atoms, which may be the same or different; Preferred R ¹³ to R ¹⁶ are a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, and a halogenated hydrocarbyl group having 1 to 20 carbon atoms.

Examples of (VH) ⁺ that is a Bronsted acid include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, and triarylphosphonium. On the other hand, examples of (BR ¹³ R ¹⁴ R ¹⁵ R ¹⁶ ) ^— include the same as those described above.

Specific examples of the boron compound (A-2-3) represented by the general formula (VH) ⁺ (BR ¹³ R ¹⁴ R ¹⁵ R ¹⁶ ) ^— include triethylammonium tetrakis (pentafluorophenyl) borate, tripropyl Ammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N, N -Dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N , N Dimethylanilinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, Examples thereof include tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, and triphenylcarbenium tetrakis (pentafluorophenyl) borate. Of these, triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate are preferable.

The contact for producing the olefin polymerization catalyst obtained by bringing the complex represented by the general formula (1) and the promoter component (A) into contact with each other is performed by the complex represented by the general formula (1) and the promoter. Any means may be used as long as it contacts the component (A) to form a catalyst. For example, a method in which the complex represented by the general formula (1) and the cocatalyst component (A) are mixed and brought into contact with each other by dilution with a solvent in advance or without dilution, and the general formula (1). A method of separately supplying the complex and the promoter component (A) to the polymerization tank and bringing them into contact with each other in the polymerization tank can be employed.
Here, the co-catalyst component (A) may be used in combination of a plurality of types, but some of them may be mixed in advance or used separately by supplying them to the polymerization tank. May be.

When the organoaluminum compound (A-1) is used as the cocatalyst component (A), the molar ratio of the organoaluminum compound (A-1) to the complex represented by the general formula (1) is, for example, 0.8. The range is from 01 to 10,000, and preferably from 1 to 5,000. In addition, when the boron compound (A-2) is used as the cocatalyst component (A), the molar ratio of the boron compound (A-2) to the complex represented by the general formula (1) is, for example, 0.8. The range is from 01 to 100, and preferably from 1.0 to 50.

When a catalyst is produced before a polymerization reaction in a polymerization reactor, the concentration of each component when supplying each component in a solution state or in a state suspended or slurried in a solvent is a device for supplying each component to the polymerization reactor. In general, the concentration of the complex represented by the general formula (1) is, for example, 0.0001 to 10000 mmol / L, more preferably 0.001 to 1000 mmol / L. More preferably, it is in the range of 0.01 to 100 mmol / L, and the concentration of the organoaluminum compound (A-1) is, for example, 0.01 to 10000 mmol / L in terms of Al atoms, more preferably 0.05 to 100 mmol / L. It is 5000 mmol / L, more preferably in the range of 0.1 to 2000 mmol / L, and the concentration of the boron compound (A-2) is, for example, 0.001. 500 mmol / L, more preferably, 0.01 ~ 250 mmol / L, more preferably, it is desirable to use each component to be in the range of 0.05 ~ 100mmol / L.

As a catalyst for olefin polymerization obtained by contacting the complex represented by the general formula (1) with at least one of the organoaluminum compound (A-1) and the boron compound (A-2), When the olefin polymerization catalyst obtained by contacting the complex represented by 1) with the organoaluminum compound (A-1) is used, the organoaluminum compound (A-1) may be the above cyclic aluminoxane (A-1). It is preferable to use at least one of -1-2) and linear aluminoxane (A-1-3). As another preferred embodiment of the olefin polymerization catalyst, an olefin polymerization catalyst obtained by contacting the complex represented by the general formula (1), the organoaluminum compound (A-1) and the boron compound (A-2). In this case, the organoaluminum compound (A-1) is easy to use the organoaluminum compound (A-1-1), and the boron compound (A-2) is a boron compound (A-2). -1) or a boron compound (A-2-2) is preferred.

[Method for producing ethylene polymer]
The method for producing an ethylene polymer of the present invention is a method in which ethylene is polymerized alone or ethylene and an α-olefin are copolymerized in the presence of the catalyst of the present invention. When ethylene is polymerized alone, polyethylene is obtained as an ethylene polymer. When ethylene and α-olefin are copolymerized, a copolymer of ethylene and α-olefin is obtained. The content of α-olefin in the copolymer of ethylene and α-olefin is less than 50 mol%, preferably 35 mol% or less, more preferably 15 mol% or less, and further preferably 10 mol% or less. . The α-olefin may be a single species or a plurality of species. By copolymerizing ethylene and a single kind of α-olefin, a copolymer of ethylene and a single kind of α-olefin can be obtained, and by polymerizing ethylene and a plurality of kinds of α-olefin, ethylene and a plurality of kinds of α-olefin can be obtained. A copolymer with α-olefin is obtained. The α-olefin compound used for the polymerization is not particularly limited, and examples thereof include monoolefins and diolefins. Examples of monoolefins include, for example, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, and vinylcyclohexane. 1-alkene (which may be branched) and the like. In addition, the monoolefin in the present specification includes styrene in which a part of hydrogen atoms of the monoolefin (for example, ethylene) is substituted with an aromatic group. Examples of diolefins include butadiene, isoprene and 1,5-hexadiene.

Specific examples of the monomer constituting the copolymer include ethylene and propylene, ethylene and 1-butene, ethylene and 1-pentene, ethylene and 1-hexene, ethylene and 1-octene, ethylene and 1-decene, and ethylene and 4 -Methyl-1-pentene, ethylene and vinylcyclohexane, ethylene and styrene, ethylene and butadiene, ethylene and isoprene, ethylene and 1,5-hexadiene, and the like. Among them, ethylene and propylene, ethylene and 1-butene, ethylene and 1-pentene, ethylene and 1-hexene, ethylene and 1-octene, ethylene and 4-methyl-1-pentene, ethylene and vinylcyclohexane, and ethylene and styrene More preferred are ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 1-octene, ethylene and vinylcyclohexane, and ethylene and styrene, and ethylene and propylene, ethylene and 1-butene, and ethylene. And 1-hexene are more preferred.

The polymerization method is not particularly limited. For example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane and octane, aromatic hydrocarbons such as benzene and toluene, or halogenated hydrocarbons such as methylene dichloride. Solvent polymerization using carbon as a solvent, slurry polymerization, or the like is possible. Further, both continuous polymerization and batch polymerization are possible.

The temperature and time of the polymerization reaction can be determined in consideration of the desired polymerization average molecular weight and the activity and amount of catalyst used. The polymerization temperature can be, for example, in the range of −50 ° C. to 200 ° C., and particularly preferably in the range of −20 ° C. to 100 ° C. The polymerization pressure is preferably normal pressure to 50 MPa. In general, the polymerization time is appropriately determined depending on the kind of the target polymer and the reaction apparatus, and can be, for example, in the range of 1 minute to 20 hours, preferably in the range of 5 minutes to 18 hours. However, it is not intended to be limited to these ranges. Moreover, in the manufacturing method of the ethylene-type polymer of this invention, in order to adjust the molecular weight of a copolymer, chain transfer agents, such as hydrogen, can also be added.

When a solvent is used for the polymerization reaction, the concentration of each compound in the solvent is not particularly limited. The concentration of the complex represented by the general formula (1) in the solvent is, for example, in the range of 1 × 10 ⁻⁸ mmol / L to 10 mol / L, and the concentration of the promoter component (A) is, for example, 1 It may be in the range of x10 ⁻⁸ mmol / L to 10 mol / L. The ratio of olefin to solvent (olefin: solvent) can be in the range of 100: 0 to 1: 1,000 by volume ratio. However, these ranges are exemplary and are not intended to be limiting. Even when no solvent is used, the concentration of each compound can be appropriately set with reference to the above range.

The polymer obtained by polymerization can separate the monomer when there is a solvent and an unreacted monomer. For example, in the case of a viscous polymer, the monomer can be removed with a vacuum pump. However, this method does not remove the catalyst. In the case of a solid polymer, the monomer can be removed by washing with methanol after the solvent is distilled off. With this method, at least a part of the catalyst is removed.

Examples will be shown below, and the embodiments of the present invention will be described in more detail. Of course, the present invention is not limited to the following examples, and it goes without saying that various aspects are possible in detail. Further, the present invention is not limited to the above-described embodiments, and various modifications can be made within the scope shown in the claims, and the present invention is also applied to the embodiments obtained by appropriately combining the disclosed technical means. It is included in the technical scope of the invention. Moreover, all the literatures described in this specification are used as reference.

(1) Melting point
A thermal analyzer was measured by the following method using a differential scanning calorimeter (Diamond DSC, Perkin Elmer).
1) Hold about 10mg of sample at 150 ° C for 5 minutes under nitrogen atmosphere
2) Cooling 150 ° C to 20 ° C (5 ° C / min) hold for 2 minutes
3) Measurement: 20 ° C to 150 ° C (5 ° C / min)
(2) Molecular weight and molecular weight distribution
The polystyrene equivalent weight average molecular chain length (Aw) and polystyrene equivalent number average molecular chain length (An) of each polymer were calculated by gel permeation chromatography (GPC) under the following measurement conditions. A calibration curve was prepared using standard polystyrene. 41.3 was used as the Q factor of polystyrene.
<Measurement conditions>
Equipment: TSK HLC-8121GPC / HT (manufactured by Tosoh Corporation)
Column: 2 TSKgel GMHHR-H (20)
Measurement temperature: 152 ° C
Solvent: o-dichlorobenzene (0.05% BHT added)
Solvent flow rate: 1 ml / min
Sample concentration: 0.05%
Column and sample for calibration: TSK standard polystyrene F-2000 to A-1000 (manufactured by Tosoh)
The weight average molecular weight (Mw) and number average molecular weight (Mn) of polyethylene are determined based on the polystyrene-converted weight average molecular chain length (Aw) and number average molecular chain length (An) measured under the above measurement conditions. The factor was calculated from the following formula with 17.7.
Molecular weight (Mw, Mn) = molecular chain length (Aw, An) × Q factor
(3) Method for calculating the number of long chain branches (LCB)
Measured under the following measurement conditions¹³In the C-NMR spectrum, when the sum of the areas of all peaks having a peak top at 5 to 50 ppm is defined as 1000, the area of the peak derived from methine carbon to which a branch having 7 or more carbon atoms is bonded is represented by 1000 carbon. The number of long-chain branches per unit (the number of branches having 7 or more carbon atoms) was used. Under the present measurement conditions, the number of long chain branches (the number of branches having 7 or more carbon atoms) was determined from the peak area having a peak top in the vicinity of 38.22 to 38.27 ppm. The peak area was in the range from the chemical shift of the valley with the peak adjacent on the high magnetic field side to the chemical shift of the valley with the peak adjacent on the low magnetic field side.
<Measurement conditions>
Equipment: AVANCE600 10mm cryoprobe manufactured by Bruker
Measuring solvent: 1,2-dichlorobenzene / 1,2-dichlorobenzene-d₄= 75/25 (volume ratio) liquid mixture
Measurement temperature: 130 ° C
Measuring method: Proton decoupling method
Pulse width: 45 degrees
Pulse repetition time: 4 seconds
Chemical shift value standard: Tetramethylsilane
(4) Calculation method of comonomer content
Ethylene / 1-hexene copolymer
Measured according to the above conditions¹³It was calculated from the C-NMR spectrum according to the method described in Analytical Chemistry, 2004, 76, 5734-5747.
(5) Calculation method of the number of terminal vinyl groups
Polyethylene measured under the following measurement conditions¹In the H NMR spectrum, when the area in the range of 0.5 to 2.5 ppm is 1000, the peak area of 4.92 to 5.20 ppm is defined as the number of terminal vinyl groups per 1000 carbons.
<¹H-NMR measurement conditions>
Device: JEOL EX-270
Measuring solvent: 1,1,2,2-tetrachloroethane-d₂
Measurement temperature: 135 ° C
Pulse width: 30 degrees
Pulse repetition time: 4 seconds
Chemical shift value standard: The peak of 1,1,2,2-tetrachloroethane was 6.0 ppm.
(6) Intrinsic viscosity ([η]) (unit: dl / g)
Measured using a Ubbelohde viscometer at a measurement temperature of 135 ° C. using tetralin as a solvent.
(Reference Example 1)
Synthesis of trans-1,2-bis (2-hydroxy-3,5-di-tert-butylbenzylsulfanyl) cyclohexane
Under an argon atmosphere, 1.08 g (7.3 mmol) of trans-cyclohexane-1,2-dithiol and 4.58 g (15.3 mmol) of 3,5-di-t-butyl-2-hydroxybenzyl bromide were added to 90 mL of tetrahydrofuran. Dissolved and cooled to 0 ° C. Triethylamine 2.13mL (15.3mmol) was added there, and it stirred at 0 degreeC for 15 hours. The formed precipitate was removed by filtration, and the filtrate was concentrated under reduced pressure. Ether and dilute hydrochloric acid were added to the obtained residue, the ether layer was washed with water and dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: hexane-dichloromethane 1: 1) to obtain 3.86 g (yield 90%) of the title compound as colorless crystals.
Melting point: 104-106 ° C decomposition (recrystallization from ethanol)
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.19-1.43 (m, 44 H), 2.09-2.15 (m, 2 H), 2.58-2.61 (m, 2 H), 3.79 (s, 4 H), 6.75 (s, 2 H), 6.93 (d, J = 2 Hz, 2 H), 7.25 (d, J = 2 Hz, 2 H).
¹³C-NMR (100.7 MHz, δ, CDCl_Three)
24.7, 29.7, 31.6, 32.6, 33.9, 34.2, 35.0, 48.1, 121.6, 123.7, 125.2, 137.3, 142.2, 152.0.
Elemental analysis: Calculated value (C₃₆H₅₆O₂S₂) C, 73.92%; H, 9.34%.
Found: C, 74.17%; H, 9.31%.
(Reference Example 2)
Synthesis of [cyclohexanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylhafnium
The following experiment was conducted in a glove box in an argon atmosphere. In a 100 mL Schlenk tube, 200.0 mg (0.342 mmol) of trans-1,2-bis (2-hydroxy-3,5-di-tert-butylbenzylsulfanyl) cyclohexane was dissolved in 10 mL of toluene. At room temperature, 10 mL of a toluene solution of 185.7 mg (0.342 mmol) of tetrabenzylhafnium was added dropwise, and the mixture was further stirred for 1 hour. Toluene was distilled off under reduced pressure, and the residue was washed 3 times with 2 mL of hexane and dried to obtain 201.3 mg (yield 62%) as a diastereomeric mixture of the title compound as colorless crystals. The diastereomeric ratio was 64/36.
Major:¹H-NMR (400 MHz, δ, ppm, CD_ThreeC₆D_Five)
1.06-1.92 (m, 44H), 2.55 (d, J = 12 Hz, 2H), 2.84 (d, J = 12 Hz, 2H), 3.21 (d, J = 14 Hz, 2H), 3.37 (d, J = 14 Hz, 2H), 6.62 (d, J = 2 Hz, 2H), 6.74-6.81 (m, 2H), 7.04-7.12 (m, 6H), 7.25 (d, J = 8 Hz, 4H), 7.54 (d, J = 2 Hz, 2H).
Minor:¹H-NMR (400 MHz, δ, ppm, CD_ThreeC₆D_Five)
1.06-1.92 (m, 44H), 2.38 (d, J = 12 Hz, 2H), 2.85 (d, J = 14Hz, 2H), 2.94 (d, J = 12 Hz, 2H), 3.18 (d, J = 14 Hz, 2H), 6.59 (d, J = 2 Hz, 2H), 6.74-6.81 (m, 2H), 7.04-7.12 (m, 6H), 7.31 (d, J = 8 Hz, 4H), 7.47 ( d, J = 2 Hz, 2H).
(Reference Example 3)
Synthesis of trans-1,2-bis (2-hydroxy-3,5-di-tert-butylbenzylsulfanyl) cyclooctane
Under argon atmosphere, 2.18 g (12.4 mmol) of trans-cyclooctane-1,2-dithiol and 7.52 g (25.1 mmol) of 3,5-di-t-butyl-2-hydroxybenzyl bromide were added to 80 mL of tetrahydrofuran. And cooled to 0 ° C. Thereto was added 3.5 mL (24.9 mmol) of triethylamine, and the mixture was stirred at 0 ° C. for 1 hour and further at room temperature overnight. The formed precipitate was removed by filtration, and the filtrate was concentrated under reduced pressure. Ether and saturated aqueous ammonium chloride solution were added to the resulting residue, and the ether layer was washed with water and dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: hexane-dichloromethane 1: 1) to obtain 6.74 g (yield 89%) of the title compound as colorless crystals.
Melting point: 122-123 ° C (recrystallized from hexane)
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.12-1.94 (m, 48 H), 2.63-2.65 (m, 2 H), 3.81 (d, J = 13 Hz, 2 H), 3.90 (d, J = 13 Hz, 2 H), 6.92 (d, J = 2 Hz, 2 H), 6.95 (s, 2 H), 7.26 (d, J = 2 Hz, 2 H).
¹³C-NMR (100.7 MHz, δ, CDCl_Three)
25.7, 25.8, 29.8, 31.2, 31.6, 34.2, 35.0, 35.4, 49.6, 121.6, 123.7, 125.4, 137.4, 142.0, 152.2.
Elemental analysis: Calculated value (C₃₈H₆₀O₂S₂) C, 74.45%; H, 9.87%.
Found: C, 74.39%; H, 10.09%.
(Reference Example 4)
Synthesis of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylhafnium
The following experiment was conducted in a glove box in an argon atmosphere. In a 50 mL Schlenk tube, 192 mg (0.313 mmol) of trans-1,2-bis (2-hydroxy-3,5-di-tert-butylbenzylsulfanyl) cyclooctane was dissolved in 10 mL of toluene. Then, 10 mL of a toluene solution of 170 mg (0.313 mmol) of tetrabenzylzirconium was added dropwise, and the mixture was further stirred for 1 hour. Toluene was distilled off under reduced pressure, and the residue was washed with 2 mL of hexane and then dried to obtain 209 mg (yield 69%) of the title compound as colorless crystals.
Melting point: 203 ° C decomposition
¹H-NMR (400 MHz, δ, ppm, C₆D₆)
1.18-1.94 (m, 48H), 2.35 (m, 2H), 2.61 (d, J = 12 Hz, 2H), 2.88 (d, J = 12 Hz, 2H), 3.13 (d, J = 14 Hz, 2 H), 3.41 (d, J = 14 Hz, 2 H), 6.62 (d, J = 2 Hz, 2H), 6.78 (t, J = 8 Hz, 2H), 7.10 (t, J = 8 Hz, 4H ), 7.29 (t, J = 8 Hz, 4 H), 7.57 (d, J = 2 Hz, 2 H)
¹³C-NMR (100.4 MHz, δ, ppm, C₆D₆)
25.1, 26.2, 28.8, 30.5, 31.8, 32.1, 34.2, 35.6, 49.1, 77.2, 121.4, 121.8, 124.6, 125.6, 126.0, 129.3, 138.5, 141.1, 148.4, 157.9.
Elemental analysis: Calculated value (C₅₂H₇₂O₂S₂Hf) C, 64.27%; H, 7.47%. Found: C, 63.87%; H, 7.59%.
(Reference Example 5)
Synthesis of trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-hydroxybenzylsulfanyl] cyclooctane
(1) Synthesis of 6- (1-adamantyl) -2- (hydroxymethyl) -p-cresol
In a nitrogen-substituted 1 L four-necked flask, 20.9 g (86.1 mmol) of 2- (1-adamantyl) -p-cresol, 16.4 g (172 mmol) of magnesium chloride, 13.0 g (433 mmol) of paraformaldehyde and 400 mL of tetrahydrofuran were added. added. Triethylamine 24mL (172mmol) was added here, and it heated and refluxed for 2.5 hours. The reaction solution was allowed to cool to room temperature, and the insoluble material was filtered off. After distilling off volatile components from the filtrate under reduced pressure, ethyl acetate was added to the residue, followed by washing with 1M HCl and saturated brine in this order. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 19.2 g of a mixture containing 2- (1-adamantyl) -5-methylsalicylaldehyde.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.78 ~ 2.25 (15H), 2.32 (s, 3H), 6.98 (d, J = 2 Hz, 1H), 7.27 (d, J = 2 Hz, 1H), 9.82 (s, 1H), 11.64 (s, 1H ).
Next, 19.2 g of the above mixture, 135 mL of tetrahydrofuran and 80 mL of methanol were added to a 500 mL four-necked flask purged with nitrogen, and cooled with ice. To this, 1.60 g (42.5 mmol) of sodium borohydride was slowly added, and the temperature was raised to room temperature, followed by stirring for 14.5 hours. After distilling off volatile components under reduced pressure, ethyl acetate was added, and the mixture was washed with 1M HCl and saturated saline in this order. The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: chloroform: hexane = 1: 3 to 1: 0) to give 6- (1-adamantyl) -2- (hydroxymethyl) -p-cresol 8 .80 g (38% yield) was obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.78 (m, 6H), 2.01 (br, 1H), 2.07 (m, 3H), 2.15 (m, 6H), 2.25 (s, 3H), 4.81 (d, J = 4 Hz, 2H), 6.70 (d , J = 2 Hz, 1H), H6.99 (d, J = 2 Hz, 1H), 7.50 (s, 1H).
(2) Synthesis of 3- (1-adamantyl) -5-methyl-2-hydroxybenzyl bromide
To a 200 mL four-necked flask purged with nitrogen, 8.80 g (32.3 mmol) of 6- (1-adamantyl) -2- (hydroxymethyl) -p-cresol and 132 mL of dichloromethane were added. To this, 15 mL of phosphorus tribromide (1.23 M dichloromethane solution, 18.5 mmol) was added, and the mixture was stirred at room temperature for 3.5 hours. The reaction solution was added to ice water, and the organic layer was washed with water and saturated brine. The organic layer was dried over anhydrous magnesium sulfate, and then the volatile component was distilled off under reduced pressure to give 11.1 g of 3- (1-adamantyl) -5-methyl-2-hydroxybenzyl bromide (crude yield: 103% ) Was obtained as a pale yellow solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.78 (m, 6H), 2.09 (m, 3H), 2.12 (m, 6H), 2.26 (s, 3H), 4.54 (s, 2H), 6.92 (d, J = 2 Hz, 1H), 7.04 (d , J = 2 Hz, 1H).
(3) Synthesis of trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-hydroxybenzylsulfanyl] cyclooctane
In a 200 mL four-necked flask purged with nitrogen, 7.04 g (21.0 mmol) of 3- (1-adamantyl) -5-methyl-2-hydroxybenzyl bromide and 1.83 g of trans-cyclooctane-1,2-dithiol ( 10.4 mmol) and 100 mL of tetrahydrofuran were added. Triethylamine 4.3mL (31mmol) was added here, and it stirred at room temperature for 21.5 hours. The reaction solution was filtered, and volatile components were distilled off from the filtrate under reduced pressure. Ethyl acetate and aqueous ammonium chloride solution were added to the resulting residue. The organic layer was further washed with an aqueous ammonium chloride solution and saturated brine in that order, and then dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, trans-1,2-bis [3- (1-adamantyl) -5 was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 20: 1). 6.61 g of a 6: 1 mixture of -methyl-2-hydroxybenzylsulfanyl] cyclooctane and trans-1- [3- (1-adamantyl) -5-methyl-2-hydroxybenzylsulfanyl] -2-sulfanylcyclooctane Got. This mixture and 1.36 g (3.98 mmol) of 3- (1-adamantyl) -5-methyl-2-hydroxybenzyl bromide were dissolved in 100 mL of tetrahydrofuran and cooled on ice. Triethylamine 0.74mL (5.31mmol) was added here, and it stirred for 15.5 hours. The reaction solution was filtered, and volatile components were distilled off from the filtrate under reduced pressure. Ethyl acetate and an aqueous ammonium chloride solution were added to the obtained residue, and the organic layer was further washed with an aqueous ammonium chloride solution and saturated brine in this order. The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 20: 1), and the obtained solid was further repulp washed with hexane at room temperature, whereby trans-1,2-bis 6.08 g (yield 85%) of [3- (1-adamantyl) -5-methyl-2-hydroxybenzylsulfanyl] cyclooctane was obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.2 ~ 2.0 (m, 12H), 1.77 (m, 12H), 2.05 (m, 6H), 2.13 (12H), 2.24 (s, 6H), 2.67 (m, 2H), 3.73 (d, J = 13 Hz , 2H), 3.82 (d, J = 13 Hz, 2H), 6.71 (d, J = 2Hz, 2H), 6.83 (s, 2H), 6.97 (d, J = 2 Hz, 2H).
(Reference Example 6)
Synthesis of {cyclooctanediyl-trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-oxoylbenzylsulfanyl]} dibenzylhafnium
Trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-hydroxybenzylsulfanyl] cyclooctane 200 mg (0.29 mmol) in toluene (6 mL) in a 50 mL Schlenk tube in a glove box under nitrogen atmosphere ) A solution of tetrabenzylhafnium 159 mg (0.29 mmol) in toluene (6 mL) was added dropwise at room temperature. After 1.5 hours, the reaction solution was filtered, and volatile components were distilled off from the filtrate under reduced pressure. The obtained residue was washed with pentane and dried under reduced pressure to obtain {cyclooctanediyl-trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-oxoylbenzylsulfanyl] } Obtained 249 mg (82% yield) of dibenzylhafnium as a white powder.
¹H-NMR (400MHz, δ, ppm, Toluene-d₈)
0.6 ~ 1.4 (m, 12H), 1.84 (m, 6 H), 2.1 ～ 2.2 (16H), 2.17 (s, 6H), 2.41 (m, 12H), 2.66 (d, J = 12 Hz, 2H), 2.83 (d, J = 12 Hz, 2H), 3.11 (d, J = 14 Hz, 2H), 3.51 (d, J = 14 Hz, 2H), 6.27 (s, 2H), 6.78 (t, J = 7 Hz, 2H), 7.1-7.2 (10H).
(Reference Example 7)
Synthesis of trans-1,2-bis (5-tert-butyl-3-cumyl-2-hydroxybenzylsulfanyl) cyclooctane
(1) Synthesis of 4-tert-butyl-2-cumylphenol
To a nitrogen-substituted 200 mL two-necked flask, 12.7 g (84.6 mmol) of 4-tert-butylphenol, 5.5 mL (42 mmol) of α-methylstyrene and 100 mL of cyclohexane were added, and the temperature was raised to 50 ° C. To this, 73 mg (0.42 mmol) of p-toluenesulfonic acid was added and stirred for 4 hours. After the reaction solution was cooled to room temperature, water and dichloromethane were added. After the organic layer was dried over anhydrous magnesium sulfate, the volatile component was distilled off under reduced pressure. The obtained colorless oil was purified by silica gel column chromatography (developing solvent: dichloromethane: heptane = 1: 3) to give 8.06 g (yield 71%) of 4-tert-butyl-2-cumylphenol as a colorless oil. Got as.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.35 (s, 9H), 1.69 (s, 6H), 4.17 (s, 1H), 6.68 (d, J = 8 Hz, 1H), 7.19 (dd, J = 2 Hz, 8 Hz, 1H), 7.2 ~ 7.3 (5H), 7.48 (d, J = 2 Hz, 1H).
¹³C {¹H} -NMR (100.4 MHz, δ, ppm, CDCl_Three)
29.6, 31.6, 34.3, 41.8, 117.1, 123.1, 124.7, 126.0, 126.9, 129.1, 134.5, 143.1, 148.5, 151.4.
(2) Synthesis of 4-tert-butyl-6-cumyl-2- (hydroxymethyl) phenol In a 200 mL two-necked flask purged with nitrogen, 7.25 g (23.3 mmol, 4-tert-butyl-2-cumylphenol, Purity 86.3%), 4.44 g (46.6 mmol) of magnesium chloride, 3.50 g (117 mmol) of paraformaldehyde and 145 mL of tetrahydrofuran were added. Triethylamine 6.5mL (47mmol) was added here, and it heated and refluxed for 3 hours. The reaction solution was allowed to cool to room temperature, and the insoluble material was filtered off. After distilling off volatile components from the filtrate under reduced pressure, ethyl acetate and water were added to the residue. The organic layer was washed with 1M HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 8.05 g of a mixture containing 5-tert-butyl-3-cumylsalicylaldehyde (purity 79.9%, yield 93%).
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.42 (s, 9H), 1.74 (s, 6H), 7.1-7.4 (5H), 7.39 (d, J = 2 Hz, 1H), 7.74 (d, J = 2 Hz, 1H), 9.81 (s, 1H ), 11.2 (s, 1H).
Next, 8.05 g of the above mixture, 40 mL of tetrahydrofuran and 40 mL of methanol were added to a 100 mL flask purged with nitrogen, and the mixture was ice-cooled. To this was slowly added 340 mg (8.97 mmol) of sodium borohydride, and the mixture was warmed to room temperature and stirred for 7 hours. After distilling off volatile components from the reaction solution under reduced pressure, water and ethyl acetate were added. The organic layer was washed with 1M HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate. After the solvent was distilled off under reduced pressure, the obtained colorless oil was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 15 to 1: 5) to give 4-tert-butyl-6. 4.88 g (yield 75%) of -cumyl-2- (hydroxymethyl) phenol were obtained as a colorless oil.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.34 (s, 9H), 1.70 (s, 6H), 2.16 (t, J = 6 Hz, 1H), 4.65 (d, J = 6 Hz, 2H), 5.56 (s, 1H), 7.09 (d, J = 2 Hz, 1H), 7.2 to 7.4 (5H), 7.45 (d, J = 2 Hz, 1H).
(3) Synthesis of 5-tert-butyl-3-cumyl-2-hydroxybenzyl bromide
4-tert-butyl-6-cumyl-2- (hydroxymethyl) phenol 4.88 g (16.4 mmol) and dichloromethane 24 mL were added to nitrogen-substituted 50 mL Schlenk. To this, 8.2 mL of phosphorus tribromide (1.0 M dichloromethane solution, 8.2 mmol) was added, and the mixture was stirred at room temperature for 1.5 hours. Water was added to the reaction solution, and the organic layer was further washed twice with water and then with saturated brine. The organic layer was dried over anhydrous magnesium sulfate, and then the volatile component was distilled off under reduced pressure, whereby 5.76 g (yield 98%) of 5-tert-butyl-3-cumyl-2-hydroxybenzyl bromide was colorless. Obtained as an oil.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.35 (s, 9H), 1.69 (s, 6H), 4.47 (s, 2H), 7.24 (d, J = 2 Hz, 1H), 7.2 ~ 7.4 (5H), 7.48 (d, J = 2 Hz, 1H ).
(4) Synthesis of trans-1,2-bis (5-tert-butyl-3-cumyl-2-hydroxybenzylsulfanyl) cyclooctane
In a 100 mL two-necked flask purged with nitrogen, 2.85 g (7.89 mmol) of 5-tert-butyl-3-cumyl-2-hydroxybenzyl bromide and 7.6 mL of trans-cyclooctane-1,2-dithiol (0. 5M tetrahydrofuran solution, 3.8 mmol) and 21 mL of tetrahydrofuran were added and ice-cooled. Triethylamine 1.1mL (7.9 mmol) was added here, and it stirred at 0 degreeC for 1 hour, and also at room temperature for 2 hours. After distilling off volatile components from the reaction solution under reduced pressure, ethyl acetate and an aqueous ammonium chloride solution were added. The organic layer was washed with water and then saturated brine, and then dried over anhydrous magnesium sulfate. After the solvent was distilled off under reduced pressure, trans-1,2-bis (5-tert-butyl-3-cumyl-) was purified by silica gel column chromatography (developing solvent: dichloromethane: hexane = 1: 1). 2.26 g of a 2: 1 mixture of 2-hydroxybenzylsulfanyl) cyclooctane and trans-1- (5-tert-butyl-3-cumyl-2-hydroxybenzylsulfanyl) -2-sulfanylcyclooctane was obtained. This mixture was dissolved in 4 mL of tetrahydrofuran, and 0.42 g (1.2 mmol) of 5-tert-butyl-3-cumyl-2-hydroxybenzyl bromide and 0.2 mL (1.4 mmol) of triethylamine were added at room temperature. After stirring for 2 hours, volatile components were distilled off under reduced pressure. Ethyl acetate and an aqueous ammonium chloride solution were added to the obtained reaction mixture, and the organic layer was further washed with water and saturated brine in this order. The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The resulting oil was purified by silica gel column chromatography (developing solvent: dichloromethane: hexane = 1: 1), whereby trans-1,2-bis (5-tert-butyl-3-cumyl-2-hydroxybenzylsulfanyl) ) 2.30 g (89% yield) of cyclooctane was obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.35 (s, 18H), 1.68 (s, 6H), 1.69 (s, 6H), 1.13 ~ 1.79 (m, 12H), 2.55 (m, 2H), 3.64 (d, J = 14 Hz, 2H), 3.68 (d, J = 14 Hz, 2H), 5.77 (s, 2H), 7.03 (d, J = 2 Hz, 2H), 7.13-7.26 (10H), 7.39 (d, J = 2 Hz, 2H).
¹³C {¹H} -NMR (100.4 MHz, δ, ppm, CDCl_Three)
25.8, 25.9, 29.4, 30.0, 31.0, 31.6, 34.0, 34.3, 42.1, 49.9, 123.1, 123.4, 125.67, 125.74, 126.0, 128.2, 136.1, 142.1, 150.2, 150.8.
(Reference Example 8)
Synthesis of [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dibenzylhafnium
In a glove box under a nitrogen atmosphere, in a 50 mL Schlenk tube, trans-1,2-bis (5-tert-butyl-3-cumyl-2-hydroxybenzylsulfanyl) cyclooctane 200 mg (0.27 mmol) in toluene (5 mL) To the solution, 147 mg (0.27 mmol) of tetrabenzylhafnium in toluene (5 mL) was added dropwise at room temperature. After 1 hour, the reaction solution was filtered, and volatile components were distilled off from the filtrate under reduced pressure. The obtained residue was washed with pentane and dried under reduced pressure to obtain [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] di 215 mg (72% yield) of benzyl hafnium was obtained as a white powder.
¹H-NMR (400MHz, δ, ppm, Toluene-d₈)
0.86-1.4 (m, 12H), 1.20 (s, 18H), 1.44 (d, J = 12 Hz, 2H), 1.85 (d, J = 12 Hz, 2H), 1.92 (s, 6H), 1.94 (s , 6H), 2.21 (m, 2H), 3.04 (d, J = 14 Hz, 2H), 3.13 (d, J = 14 Hz, 2H), 6.62 (d, J = 8 Hz, 2H), 6.74 (t , J = 8 Hz, 2H), 6.89 (d, J = 8 Hz, 4H), 7.05-7.16 (4H), 7.25 (t, J = 8 Hz, 4H), 7.40 (d, J = 8 Hz, 4H ), 7.52 (d, J = 2 Hz, 2H).
(Reference Example 9)
Synthesis of trans-1,2-bis [5-tert-butyl-3- (1,1-diphenylethyl) -2-hydroxybenzylsulfanyl] cyclooctane
(1) Synthesis of 4-tert-butyl-2- (1,1-diphenylethyl) phenol
4-tert-butylphenol 6.25 g (41.6 mmol), 1,1-diphenylethylene 4.9 mL (28 mmol) and cyclohexane 100 mL were added to a nitrogen-substituted 200 mL two-necked flask, and the temperature was raised to 50 ° C. Where FeCl₃0.45 g (2.8 mmol) was added and stirred for 7 hours. After the reaction solution was cooled to room temperature, water and dichloromethane were added. After the organic layer was dried over anhydrous magnesium sulfate, the volatile component was distilled off under reduced pressure. By purifying the obtained brown oil by silica gel column chromatography (developing solvent: ethyl acetate: heptane = 30: 1), 4.71 g (yield) of 4-tert-butyl-2- (1,1-diphenylethyl) phenol was obtained. 51%) was obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.17 (s, 9H), 2.22 (s, 3H), 4.35 (s, 1H), 6.73 (d, J = 8 Hz, 1H), 6.88 (d, J = 2 Hz, 1H), 7.1-7.3 (11H ).
¹³C {¹H} -NMR (100.4 MHz, δ, ppm, CDCl_Three)
28.8, 31.4, 34.1, 51.3, 117.1, 124.9, 126.5, 126.7, 128.3, 128.5, 133.7, 143.0, 146.6, 151.6.
(2) Synthesis of 4-tert-butyl-6- (1,1-diphenylethyl) -2- (hydroxymethyl) phenol
In a 200 mL two-necked flask purged with nitrogen, 4.60 g (13.9 mmol) of 5-tert-butyl-2- (1,1-diphenylethyl) phenol, 3.98 g (41.8 mmol) of magnesium chloride, and paraformaldehyde 2. 09 g (69.6 mmol) and 92 mL of tetrahydrofuran were added. Triethylamine 3.9mL (28mmol) was added here, and it heated and refluxed for 2 hours. The reaction solution was allowed to cool to room temperature, and the insoluble material was filtered off. After distilling off volatile components from the filtrate under reduced pressure, ethyl acetate and water were added to the residue. The organic layer was washed with 1M HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 5.1 g of a mixture containing 4-tert-butyl-3- (1,1-diphenylethyl) salicylaldehyde.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.14 (s, 9H), 1.55 (s, 3H), 6.6-7.4 (12H), 9.88 (s, 1H), 11.45 (s, 1H).
Next, 5.1 g of the above mixture, 26 mL of tetrahydrofuran and 26 mL of methanol were added to a nitrogen-substituted 50 mL flask, and the mixture was ice-cooled. To this, 0.27 g (7.1 mmol) of sodium borohydride was slowly added, and the temperature was raised to room temperature, followed by stirring overnight. After distilling off the volatile components under reduced pressure, water and ethyl acetate were added. The organic layer was washed with 1M HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate. After the solvent was distilled off under reduced pressure, the obtained colorless oil was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 15 to 1: 5) to give 4-tert-butyl-6. There was obtained 4.35 g (yield 85%) of-(1,1-diphenylethyl) -2- (hydroxymethyl) phenol as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.14 (s, 9H), 2.18 (t, J = 6 Hz, 1H), 2.26 (s, 3H), 4.73 (d, J = 6 Hz, 2H), 5.99 (s, 1H), 6.76 (d, J = 2 Hz, H1H), 7.07 (d, J = 2 Hz, 1H), 7.1 to 7.3 (10H).
(3) Synthesis of 5-tert-butyl-3- (1,1-diphenylethyl) -2-hydroxybenzyl bromide
4-tert-butyl-6- (1,1-diphenylethyl) -2- (hydroxymethyl) phenol 4.35 g (12.1 mmol) and dichloromethane 22 mL were added to nitrogen-substituted 50 mL Schlenk. To this, 12.1 mL of phosphorus tribromide (1.0 M dichloromethane solution, 12.1 mmol) was added, and the mixture was stirred at room temperature for 1.5 hours. Water was added to the reaction solution, and the organic layer was further washed twice with water and then with saturated brine. After drying the organic layer with anhydrous magnesium sulfate, 4.51 g of 5-tert-butyl-3- (1,1-diphenylethyl) -2-hydroxybenzyl bromide was removed by distilling off the volatile components under reduced pressure. Yield 88%) was obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.17 (s, 9H), 2.21 (s, 3H), 4.54 (s, 2H), 6.87 (d, J = 2 Hz, 1H), 7.2 ～ 7.3 (m, 11H).
(4) Synthesis of trans-1,2-bis [5-tert-butyl-3- (1,1-diphenylethyl) -2-hydroxybenzylsulfanyl] cyclooctane
In a 100 mL two-necked flask purged with nitrogen, 0.55 g (1.3 mmol) of 5-tert-butyl-3- (1,1-diphenylethyl) -2-hydroxybenzyl bromide and trans-cyclooctane-1,2 -Dithiol 1.2mL (0.5M tetrahydrofuran solution, 0.6mmol) and tetrahydrofuran 21mL were added. Triethylamine 0.17mL (1.2mmol) was added here, and it stirred at room temperature for 2 hours. After evaporating volatile components under reduced pressure, ethyl acetate and an aqueous ammonium chloride solution were added. The organic layer was washed with water and then saturated brine, and then dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, it was purified by silica gel column chromatography (developing solvent: dichloromethane: hexane = 1: 1) to obtain trans-1,2-bis [5-tert-butyl-3- (1 , 1-diphenylethyl) -2-hydroxybenzylsulfanyl] cyclooctane (0.50 g, purity 83%, yield 78%) was obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.10 (s, 18H), 2.26 (s, 6H), 1.2 ~ 1.9 (m, 12H), 2.68 (m, 2H), 3.74 (d, J = 14 Hz, 2H), 3.79 (d, J = 14 Hz , 2H), 6.07 (s, 2H), 6.64 (d, J = 2 Hz, 2H), 7.02 (d, J = 2 Hz, 2H), 7.16-7.31 (20H).
(Reference Example 10)
Synthesis of {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (1,1-diphenylethyl) -2-oxoylbenzylsulfanyl]} dibenzylhafnium
In a glove box under a nitrogen atmosphere, 50 mg of a trans-1,2-bis [5-tert-butyl-3- (1,1-diphenylethyl) -2-hydroxybenzylsulfanyl] cyclooctane (purity 83) was added to a 50 mL Schlenk tube. %, 0.06 mmol) and 32 mg (0.06 mmol) of tetrabenzylhafnium were added, and 1.2 mL of toluene was added thereto and stirred at room temperature. After 1 hour, the reaction solution was filtered, and volatile components were distilled off from the filtrate under reduced pressure. The obtained residue was washed with pentane and dried under reduced pressure to obtain {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (1,1-diphenylethyl) -2- Oxoylbenzylsulfanyl]} dibenzylhafnium 36 mg (51% yield) was obtained as a white powder.
¹H-NMR (400MHz, δ, ppm, Toluene-d₈)
0.80 ～ 1.69 (m, 12H), 1.04 (s, 18H), 1.69 (s, 4H), 2.32 (m, 2H), 2.62 (s, 6H), 3.13 (d, J = 14 Hz, 2H), 3.22 (d, J = 14 Hz, 2H), 6.61 (d, J = 8 Hz, 2H), 6.73 (d, J = 2Hz, 2H), 6.78 (t, J = 8 Hz, 2H), 6.89 (d, J = 8 Hz, 4H), 7.1 ～ 7.3 (14H).
(Reference Example 11)
Synthesis of trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (triphenylmethyl) benzylsulfanyl] cyclooctane
(1) Synthesis of 4-tert-butyl-2- (triphenylmethyl) phenol
4-tert-butylphenol 3.23 g (21.5 mmol) and triphenylmethyl chloride 2.00 g (7.17 mmol) were added to a nitrogen-substituted 100 mL Schlenk tube, and the temperature was raised to 200 ° C. After 1.5 hours, the reaction mixture was cooled to room temperature, and then the resulting solid was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 20) to give 4-tert-butyl-2- 1.28 g (45% yield) of (triphenylmethyl) phenol was obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.13 (s, 9H), 4.32 (s, 1H), 6.76 (d, J = 8 Hz, 1H), 7.07 (d, J = 2 Hz, 1H), 7.2 ~ 7.3 (16H).
(2) Synthesis of 4-tert-butyl-2-hydroxymethyl-6- (triphenylmethyl) phenol
To a 100 mL two-necked flask purged with nitrogen, 1.20 g (3.06 mmol) of 4-tert-butyl-2- (triphenylmethyl) phenol, 0.58 g (6.1 mmol) of magnesium chloride, 0.46 g (15 mmol) of paraformaldehyde ) And 24 mL of tetrahydrofuran were added. Triethylamine 0.85mL (6.1mmol) was added here, and it heated and refluxed for 8 hours. The reaction solution was allowed to cool to room temperature, and the insoluble material was filtered off. After distilling off volatile components from the filtrate under reduced pressure, ethyl acetate and water were added to the residue. The organic layer was washed with 1M HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 1.36 g of a mixture containing 5-tert-butyl-3- (triphenylmethyl) salicylaldehyde (purity 85.1%, yield 90%).
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.19 (s, 9H), 7.1-7.4 (15H), 7.44 (d, J = 2 Hz, 1H), 7.60 (d, J = 2 Hz, 1H), 9.84 (s, 1H), 11.18 (s, 1H ).
Next, 1.36 g of the above mixture, 7 mL of tetrahydrofuran and 7 mL of methanol were added to a 50 mL flask purged with nitrogen, and the mixture was ice-cooled. To this, 0.14 g (3.8 mmol) of sodium borohydride was slowly added, and the temperature was raised to room temperature, followed by stirring for 2.5 hours. After distilling off the volatile components under reduced pressure, water and ethyl acetate were added. The organic layer was washed with 1M HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 1.36 g (99% yield) of 4-tert-butyl-2-hydroxymethyl-6- (triphenylmethyl) phenol as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.15 (s, 9H), 2.04 (s, 1H), 4.65 (s, 2H), 5.18 (s, 1H), 7.07 (d, J = 2 Hz, 1H), 7.1 ~ 7.3 (15H).
(3) Synthesis of 5-tert-butyl-2-hydroxy-3- (triphenylmethyl) benzyl bromide
4-tert-butyl-2-hydroxymethyl-6- (triphenylmethyl) phenol 1.35 g (3.19 mmol) and dichloromethane 7 mL were added to nitrogen-substituted 50 mL Schlenk. To this, 1.6 mL of phosphorus tribromide (1.0 M dichloromethane solution, 1.6 mmol) was added, and the mixture was stirred at room temperature for 1.5 hours. Water was added to the reaction solution, and the organic layer was further washed twice with water and then with saturated brine. The organic layer was dried over anhydrous magnesium sulfate, and the volatile component was distilled off under reduced pressure to obtain 1.43 g of 5-tert-butyl-2-hydroxy-3- (triphenylmethyl) benzyl bromide (yield 92 %) As a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.15 (s, 9H), 4.50 (s, 2H), 7.1 ～ 7.3 (m, 17H).
(4) Synthesis of trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (triphenylmethyl) benzylsulfanyl] cyclooctane
In a 100 mL two-necked flask purged with nitrogen, 1.43 g (2.94 mmol) of 5-tert-butyl-2-hydroxy-3- (triphenylmethyl) benzyl bromide and trans-cyclooctane-1,2-dithiol 2 8 mL (0.5 M tetrahydrofuran solution, 1.4 mmol) and 11 mL of tetrahydrofuran were added. Triethylamine 0.39mL (2.8mmol) was added here, and it stirred at room temperature for 2 hours. After distilling off volatile components from the reaction solution under reduced pressure, ethyl acetate and an aqueous ammonium chloride solution were added. The organic layer was washed with water and saturated brine in that order, and then dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, trans-1,2-bis (5-tert-butyl-2-hydroxy-) was purified by silica gel column chromatography (developing solvent: dichloromethane: hexane = 1: 1). A 1: 1 mixture of 3- (triphenylmethyl) benzylsulfanyl) cyclooctane and trans-1- (5-tert-butyl-2-hydroxy-3- (triphenylmethyl) benzylsulfanyl) -2-sulfanylcyclooctane 1.12 g was obtained. This mixture was dissolved in 8 mL of tetrahydrofuran, and 0.42 g (0.87 mmol) of 5-tert-butyl-3-cumyl-2-hydroxybenzyl and 0.18 mL (1.3 mmol) of triethylamine were added at room temperature. After stirring for 2 hours, volatile components were distilled off under reduced pressure. Ethyl acetate and an aqueous ammonium chloride solution were added to the obtained reaction mixture, and the organic layer was further washed with water and saturated brine in this order. The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was purified by silica gel column chromatography (developing solvent: dichloromethane: hexane = 1: 1) to obtain trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (triphenyl). Methyl) benzylsulfanyl] cyclooctane 1.36 g (98% yield) was obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.12 (s, 18H), 1.1-1.8 ～ (m, 12H), 2.63 (m, 2H), 3.69 (s, 4H), 5.44 (s, 2H), 7.05 (d, J = 2 Hz, 2H), 7.1 ~ 7.3 (m, 32H).
(Reference Example 12)
Synthesis of {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dibenzylhafnium
In a glove box under a nitrogen atmosphere, 200 mg (0.20 mmol) of trans-1,2-bis (5-tert-butyl-2-hydroxy-3- (triphenylmethyl) benzylsulfanyl) cyclooctane was obtained with a 50 mL Schlenk tube. To a toluene (4 mL) solution was added dropwise a solution of tetrabenzylhafnium 110 mg (0.14 mmol) in toluene (4 mL) at room temperature. After 7 hours, the reaction solution was filtered, and volatile components were distilled off from the filtrate under reduced pressure. The obtained residue was washed with pentane and dried under reduced pressure to obtain {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl ] 145 mg (53% yield) of dibenzylhafnium was obtained as a white powder.
¹H-NMR (400MHz, δ, ppm, Toluene-d₈)
0.63 ~ 1.43 (m, 12H), 1.14 (s, 18H), 1.49 (d, J = 12 Hz, 2H), 1.54 (d, J = 12 Hz, 2H), 2.03 (m, 2H), 3.05 (d , J = 14 Hz, 2H), 3.34 (d, J = 14 Hz, 2H), 6.70 (d, J = 8Hz, 4H), 6.76 (d, J = 2Hz, 2H), 6.81 (t, J = 8 Hz, 2H), 7.0 to 7.7 (26H).
(Reference Example 13)
Synthesis of trans-1,2-bis [5-tert-butyl-3- (3, 5-dimethyl-1-adamantyl) -2-hydroxybenzylsulfanyl] cyclooctane
(1) Synthesis of 4-tert-butyl-2- (3, -5-dimethyl-1-adamantyl) phenol
Nitrogen-substituted 50 mL Schlenk was added with 3.3 g (22 mmol) of 4-tert-butylphenol, 4.0 g (22 mmol) of 3,5-dimethyl-1-adamantanol and 20 mL of dichloromethane, and cooled to 0 ° C. in an ice bath. To this was added 1.2 mL (22 mmol) of sulfuric acid, and the mixture was stirred at room temperature for 1 hour. The reaction solution was poured into an aqueous sodium bicarbonate solution. After the organic layer was dried over anhydrous magnesium sulfate, the volatile component was distilled off under reduced pressure. The obtained white solid is purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 10) to give 4.0 g of 4-tert-butyl-2- (3, 5-dimethyl-1-adamantyl) phenol (Yield 59%) was obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.874 (s, 6H), 1.20 (s, 2H), 1.29 (s, 9H), 1.35-1.45 (m, ～ 4H), 1.70-1.78 (m, 4H), 1.95 (m, 2H), 2.17 (m, 1H), 4.56 (s, 1H), 6.56 (d, J = 8 Hz, 1H), 7.06 (dd, J = 2 Hz, 8 Hz, 1H), 7.24 (d, J = 2 Hz, 1H).
(2) Synthesis of 4-tert-butyl-6- (3, 5-dimethyl-1-adamantyl) -2-hydroxymethylphenol
In a 100 mL two-necked flask purged with nitrogen, 4.0 g (13 mmol) of 4-tert-butyl-2- (3,5-dimethyl-1-adamantyl) phenol, 4.8 g (50 mmol) of magnesium chloride, 2.1 g of paraformaldehyde (70 mmol) and 50 mL of tetrahydrofuran were added. Triethylamine 6.7mL (48mmol) was added here, and it heated and refluxed for 3 hours. The reaction solution was allowed to cool to room temperature, and the insoluble material was filtered off. After distilling off volatile components from the filtrate under reduced pressure, ethyl acetate and water were added to the residue. The organic layer was washed with 1M HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 4.2 g of a mixture containing 5-tert-butyl-3- (3, 5-dimethyl-1-adamantyl) salicylaldehyde (yield 96%).
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.874 (s, 6H), 1.2-2.2 (m, 22H), 7.32 (d, J = 2 Hz, 1H), 7.53 (d, J = 2 Hz, 1H), 9.85 (s, 1H), 11.7 (s , 1H).
To a 100 mL flask purged with nitrogen, 4.2 g of the above mixture, 20 mL of tetrahydrofuran and 20 mL of methanol were added and cooled on ice. To this, 490 mg (13 mmol) of sodium borohydride was slowly added, and the temperature was raised to room temperature, followed by stirring for 1 hour. After distilling off volatile components from the reaction solution under reduced pressure, water and ethyl acetate were added. The organic layer was washed with 1M HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, the obtained colorless oil was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 10 to 1: 5) to give 4-tert-butyl-6- 3.4 g (yield 81%) of (3, 5-dimethyl-1-adamantyl) -2-hydroxymethylphenol was obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.875 (s, 6H), 1.2-2.2 ～ (m, 23H), 4.85 (d, J = 5 Hz, 2H), 6.88 (d, J = 2 Hz, 1H), 7.22 (d, J = 2 Hz, 1H ), 7.55 (s, 1H).
(3) Synthesis of 5-tert-butyl-3- (3, 5-dimethyl-1-adamantyl) -2-hydroxybenzyl bromide
To a 200 mL flask purged with nitrogen, 3.4 g (9.9 mmol) of 4-tert-butyl-6- (3,5-dimethyl-1-adamantyl) -2-hydroxymethylphenol and 20 mL of dichloromethane were added. To this was added 6.6 mL of phosphorus tribromide (1.0 M dichloromethane solution, 6.6 mmol), and the mixture was stirred at room temperature for 1 hour. Water was added to the reaction solution, and the organic layer was further washed twice with water and then with saturated brine. After drying the organic layer with anhydrous magnesium sulfate, the volatile component was distilled off under reduced pressure to give 5-tert-butyl-3- (3, 5-dimethyl-1-adamantyl) -2-hydroxybenzyl bromide 3 Obtained .95 g (yield 98%) as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.882 (s, 6H), 1.22 (s, 2H), 1.28 (s, ～ 9H), 1.35 to 1.45 (m, 4H), 1.70 to 1.78 (m, 4H), 1.96 (m, 2H), 2.19 (m, 1H), 4.57 (s, 1H), 7.08 (d, J = 2 Hz, 1H), 7.27 (d, J = 2 Hz, 1H).
(4) Synthesis of trans-1,2-bis (5-tert-butyl-3- (3, 5-dimethyl-1-adamantyl) -2-hydroxybenzylsulfanyl) cyclooctane
Nitrogen-substituted 50 mL Schlenk was added to 5-tert-butyl-3- (3, 5-dimethyl-1-adamantyl) -2-hydroxybenzyl bromide 1.0 g (2.5 mmol), trans-cyclooctane-1,2 -Dithiol (0.18 g, 1.0 mmol) and tetrahydrofuran (7 mL) were added, and the mixture was ice-cooled. Triethylamine 0.7mL (5.0mmol) was added here, and it stirred at 0 degreeC for 1 hour, and 2 hours at room temperature. Further, 0.05 g (0.013 mmol) of 5-tert-butyl-2-hydroxy-3- (3, 5-dimethyl-1-adamantyl) benzyl bromide was added, and the mixture was stirred at room temperature for 1 hour. After distilling off volatile components from the reaction solution under reduced pressure, ethyl acetate and an aqueous ammonium chloride solution were added. The organic layer was washed with water and saturated brine in that order, and then dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, it was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 10) to obtain trans-1,2-bis (5-tert-butyl-3- ( 1.0 g (yield -1-> 99%) of 3, 5-dimethyl-1-adamantyl) -2-hydroxybenzylsulfanyl) cyclooctane was obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.88 (s, 12H), 1.2-2.2 ～ (m, 56H), 2.59 (m, 2H), 3.77 (d, J = 14 Hz, 2H), 3.87 (d, J = 14 Hz, 2H), 6.89 (d , J = 2 Hz, 2H), 7.19 (d, J = 2 Hz, 2H).
(Reference Example 14)
Synthesis of {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3, 5-dimethyl-1-adamantyl) -2-oxoylbenzylsulfanyl]} dichlorohafnium
Trans-1,2-bis (5-tert-butyl-3- (3, 5-dimethyl-1-adamantyl) -2-hydroxybenzylsulfanyl) cyclooctane 83 in a 50 mL Schlenk tube in a glove box under nitrogen atmosphere To a solution of mg (0.10 mmol) in toluene (1 mL), dichloro {1,1'-oxybis [ethane] [bis (phenylmethyl) hafnium]} 51 mg (0.10 mmol) in toluene (1 mL) at room temperature It was dripped. After 1.5 hours, volatile components were distilled off under reduced pressure. The obtained residue was washed with pentane and dried under reduced pressure to obtain {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3, 5-dimethyl-1-adamantyl)] 2-Oxoylbenzylsulfanyl]} dichlorohafnium-55 mg mg (51% yield) was obtained as a white powder.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.901 (s, 12H), 1.0-2.4 ～ (m, 56H), 2.58 (brs, 2H), 3.88 (d, J = 14 Hz, 2H), 4.54 (d, J = 14 Hz, 2H), 6.85 (d , J = 2 Hz, 2H), 7.37 (d, J = 2 Hz, 2H).
(Reference Example 15)
Synthesis of trans-1,2-bis [5-tert-butyl-3- (2-phenyl-2-butyl) -2-hydroxybenzylsulfanyl] cyclooctane
(1) Synthesis of 4-tert-butyl-2- (2-phenyl-2-butyl) phenol
4-tert-butylphenol 6.6 g (44 mmol), 2-phenyl-2-butanol 3.4 mL (22 mmol) and heptane 20 mL were added to nitrogen-substituted 50 mL Schlenk and heated to 80 ° C. To this was added 73 mg (0.38 mmol) of p-toluenesulfonic acid monohydrate, and the mixture was stirred at 100 ° C. for 11.5 hours. Water and ethyl acetate were added to the reaction solution. After the organic layer was dried over anhydrous magnesium sulfate, the volatile component was distilled off under reduced pressure. The obtained white solid was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 10) to give 4.4 tert g of 4-tert-butyl-2- (2-phenyl-2-butyl) phenol (yield) 71%) was obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.683 (t, J = 7Hz, 3H), 1.35 (s, 9H), 1.61 (s, 3H), 2.02-2.26 (m, 2H), 4.18 (s, 1H), 6.66 (d, J = 8 Hz, 1H), 7.15-7.38 (m, 6H), 7.44 (d, J = 2 Hz, 1H).
(2) Synthesis of 4-tert-butyl-6- (2-phenyl-2-butyl) -2-hydroxymethylphenol
In a 500 mL flask purged with nitrogen, 3.0 g (11 mmol) of 4-tert-butyl-2- (2-phenyl-2-butyl) phenol, 4.0 g (41 mmol) of magnesium chloride, 1.8 g (60 mmol) of paraformaldehyde And 45 mL of tetrahydrofuran was added. Triethylamine (5.6 mL, 41 mmol) was added thereto, and the mixture was heated to reflux for 3 hours. The reaction solution was allowed to cool to room temperature, and the insoluble material was filtered off. After distilling off volatile components from the filtrate under reduced pressure, ethyl acetate and water were added to the residue. The organic layer was washed with 1M HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 2.7 g of a mixture containing 5-tert-butyl-3- (2-phenyl-2-butyl) salicylaldehyde (yield 77%).
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.882 (t, J = 7 Hz, 3H), 1.34 ~ 1.55 (m, 11H), 1.83 (s, 6H), 7.2 ~ 7.9 (m, 7H), 9.82 (s, 1H), 11.2 (s, 1H) .
2.7 mLg of the above mixture, 15 mL of tetrahydrofuran and 15 と mL of methanol were added to a 200 mL flask purged with nitrogen. To this was slowly added 340 mg (8.9 mmol) of sodium borohydride, and the mixture was warmed to room temperature and stirred for 1 hour. After distilling off volatile components from the reaction solution under reduced pressure, water and ethyl acetate were added. The organic layer was washed with 1M HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, the resulting colorless oil was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 10 to 1: 3) to give 4-tert-butyl-6- 2.1 g (yield 79%) of (2-phenyl-2-butyl) -2-hydroxymethylphenol was obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.685 (t, J = 8 Hz, 3H), 1.34 (s, 9H), 1.62 (s, 6H), 2.0 ~ 2.4 (m, 3H), 4.62 (d, J = 6 Hz, 2H), 5.38 (s , 1H), 7.0-7.5 (m, 7H).
(3) Synthesis of 5-tert-butyl-3- (2-phenyl-2-butyl) -2-hydroxybenzyl bromide
4-tert-butyl-6- (2-phenyl-2-butyl) -2-hydroxymethylphenol (2.1 g, 6.7 mmol) and dichloromethane (15 ml) were added to a nitrogen-substituted 500 mL flask. To this was added 4.5 mL of phosphorus tribromide (1.0 M dichloromethane solution, 4.5 mmol), and the mixture was stirred at room temperature for 1 hour. Water was added to the reaction solution, and the organic layer was further washed twice with water and then with saturated brine. After drying the organic layer over anhydrous magnesium sulfate, the volatile component was distilled off under reduced pressure to give 2.5 g of tert-butyl-3- (2-phenyl-2-butyl) -2-hydroxybenzyl bromide ( Yield> 99%) was obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.669 (t, J = 8 Hz, 3H), 1.35 (s, 9H), 1.61 (s, 6H), 2.0 ~ 2.3 (m, 2H), 4.46 (m, 2H), 7.2 ~ 7.5 (m, 7H) .
(4) Synthesis of trans-1,2-bis [5-tert-butyl-3- (2-phenyl-2-butyl) -2-hydroxybenzylsulfanyl] cyclooctane
In a 50-mL flask purged with nitrogen, 0.94- g (2.5 mmol) bromide, 5-tert-butyl-3- (2-phenyl-2-butyl) -2-hydroxybenzyl bromide, trans-cyclooctane-1,2-dithiol 90 mg (0.50 mmol) and 7 mL of tetrahydrofuran were added and ice-cooled. Triethylamine 0.70 mL (5.1 mmol) was added thereto, and the mixture was stirred at 0 ° C for 1 hour and at room temperature for 1 hour. Further, trans-cyclooctane-1,2-dithiol (90 mg, 0.50 mmol) was added and stirred at room temperature for 1 hour. Volatile components were distilled off under reduced pressure, and ethyl acetate and an aqueous ammonium chloride solution were added to the resulting residue. The organic layer was further washed with an aqueous ammonium chloride solution and saturated brine in that order, and then dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, it was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 10) to obtain trans-1,2-bis [5-tert-butyl-3- ( 2-Phenyl-2-butyl) -2-hydroxybenzylsulfanyl] cyclooctane (0.8 g, yield> 99%) was obtained as a pale yellow solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.663 (t, J = 8 Hz, 3H), 1.1 to 2.6 (m, 48H), 3.65 (m, 4H), 5.60 to 5.71 (m, 2H), 7.0 to 7.4 (m, 14H).
(Reference Example 16)
Synthesis of {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (2-phenyl-2-butyl) -2-oxoylbenzylsulfanyl]} dichlorohafnium
In a glove box under a nitrogen atmosphere, trans-1,2-bis [5-tert-butyl-3- (2-phenyl-2-butyl) -2-hydroxybenzylsulfanyl] cyclooctane 150 mg in a 50 mL Schlenk tube ( To a solution of 0.20 mmol) in toluene (1 mL), dichloro {1,1'-oxybis [ethane] [bis (phenylmethyl) hafnium]} 110 mg (0.20 mmol) in toluene (1 mL) was added dropwise at room temperature. . After 1.5 hours, volatile components were distilled off under reduced pressure. The obtained residue was washed with pentane and dried under reduced pressure to obtain {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (2-phenyl-2-butyl) -2 -Oxoylbenzylsulfanyl]} dichlorohafnium-97 mg mg (48% yield) was obtained as a white powder.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.7 ~ 2.2 (m, 46H), 2.47 (m, 1H), 3.20 (m, 1H), 3.54 (m, 2H), 4.08 (m, 2H), 6.82 (s, 2H), 7.0 ～ 7.5 (m, 10H).
(Reference Example 17)
Synthesis of trans-1,2-bis (3-tert-amyl-5-tert-butyl-2-hydroxybenzylsulfanyl) cyclooctane
(1) Synthesis of 2-tert-amyl-4-tert-butylphenol
4-tert-butylphenol 3.3 g (22 mmol), tert-amyl alcohol 2.4 および mL (22 mmol) and dichloromethane 20 ジクロロメタン mL were added to nitrogen-substituted 50 mL Schlenk, and cooled to 0 ° C in an ice bath. To this was added 1.2 mL (22 mmol) of sulfuric acid and stirred at room temperature for 20 minutes. The reaction solution was poured into an aqueous sodium bicarbonate solution. After the organic layer was dried over anhydrous magnesium sulfate, the volatile component was distilled off under reduced pressure. The obtained white solid was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 10) to give 3.7 g of 2-tert-amyl-4-tert-butylphenol (yield 75%) as a colorless oil. Obtained.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.682 (t, J = 8 Hz, 3H), 1.29 (s, 9H), 1.37 (s, 6H), 1.84 (q, J = 8 Hz, 2H), 4.57 (s, 1H), 6.57 (d, J = 8 Hz, 1H), 7.06 (dd, J = 2 Hz, 8 Hz, 1H), 7.23 (d, J = 2 Hz, 1H).
(2) Synthesis of 6-tert-amyl-4-tert-butyl-2-hydroxymethylphenol
In a 200 mL four-necked flask purged with nitrogen, 3.7 g (17 mmol) of 2-tert-amyl-4-tert-butylphenol, 3.2 g (33 mmol) of magnesium chloride, 2.5 g (83 mmol) of paraformaldehyde and 75 mL of tetrahydrofuran added. To this was added 4.6 mL (33 mmol) of triethylamine, and the mixture was heated to reflux for 1.5 hours. The reaction solution was allowed to cool to room temperature, and the insoluble material was filtered off. After distilling off volatile components from the filtrate under reduced pressure, ethyl acetate and water were added to the residue. The organic layer was washed with 1M HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 3.9 g of a mixture containing 3-tert-amyl-5-tert-butylsalicylaldehyde (yield 94%).
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.648 (t, J = 8 Hz, 3H), 1.28 (s, 9H), 1.37 (s, 6H), 1.90 (q, J = 8 Hz, 2H), 7.33 (d, J = 2 Hz, 1H), 7.54 (d, J = 2 Hz, 1H), 9.86 (s, 1H), H11.6 (s, 1H).
To a 200 mL four-necked flask purged with nitrogen, 3.9 μg of the above mixture, 40 μmL of tetrahydrofuran, and 20 μmL of methanol were added and cooled on ice. To this was slowly added 360 mg (9.5 mmol) of sodium borohydride, and the mixture was warmed to room temperature and stirred for 15 hours. After distilling off volatile components from the reaction solution under reduced pressure, water and ethyl acetate were added. The organic layer was washed with 1M HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, the obtained colorless oil was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 20 to 1: 9) to give 6-tert-amyl-4- 2.4 g of tert-butyl-2-hydroxymethylphenol (yield 61%) was obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.681 (t, J = 7 Hz, 3H), 1.28 (s, 9H), 1.38 (s, 6H), 1.90 (q, J = 7 Hz, 2H), 4.84 (s, 2H), 6.88 (d, J = 2 Hz, 1H), 7.21 (d, J = 2 Hz, 1H), 7.48 (s, 1H).
(3) Synthesis of 3-tert-amyl-5-tert-butyl-2-hydroxybenzyl bromide
To a 200 mL four-necked flask purged with nitrogen, 2.4 g (9.4 と mmol) of 6-tert-amyl-4-tert-butyl-2-hydroxymethylphenol and 40 mL of dichloromethane were added. To this was added 5.7 mL of phosphorus tribromide (1.0 M M dichloromethane solution, 5.7 M mmol), and the mixture was stirred at room temperature for 3.5 hours. Water was added to the reaction solution, and the organic layer was further washed twice with water and then with saturated brine. After drying the organic layer over anhydrous magnesium sulfate, the volatile components are distilled off under reduced pressure to give 3.2 g of tert-amyl bromide-2-tert-butyl-2-hydroxybenzyl bromide (yield> 99%) Was obtained as a pale yellow oil.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.676 (t, J = 8 Hz, 3H), 1.29 (s, 9H), 1.37 (s, 6H), 1.86 (q, J = 7 Hz, 2H), 4.58 (s, 2H), 7.09 (d, J = 2 Hz, 1H), 7.26 (d, J = 2 Hz, 1H).
(4) Synthesis of trans-1,2-bis (3-tert-amyl-5-tert-butyl-2-hydroxybenzylsulfanyl) cyclooctane
In a nitrogen-substituted 50 mL 4-necked flask, 、 3-tert-amyl-5-tert-butyl-2-hydroxybenzyl bromide 1.4 g (4.5 mmol), trans-cyclooctane-1,2-dithiol 0.40 g (2.2 mmol) ) And 22 mL of tetrahydrofuran were added and cooled on ice. Triethylamine 1.0 mL (7.2 mmol) was added thereto and stirred at room temperature for 22.5 hours. The reaction solution was filtered, and volatile components were distilled off from the filtrate under reduced pressure. Ethyl acetate and aqueous ammonium chloride solution were added to the resulting residue. The organic layer was further washed with an aqueous ammonium chloride solution and saturated brine in that order, and then dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, it was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 20) to obtain trans-1,2-bis (3-tert-amyl-5-tert -Butyl-2-hydroxybenzylsulfanyl) cyclooctane and trans-1- (3-tert-amyl-5-tert-butyl-2-hydroxybenzylsulfanyl) -2-sulfanylcyclooctane 1.5: 1 g of a 6: 1 mixture Obtained. This mixture and 0.20 g (0.64 mmol) of tert-amyl-5-tert-butyl-2-hydroxybenzyl bromide were dissolved in 100 mL of tetrahydrofuran and cooled on ice. To this was added 0.12 mL (0.86 mmol) of triethylamine, and the mixture was stirred for 22.5 hours. The reaction solution was filtered, and volatile components were distilled off from the filtrate under reduced pressure. Ethyl acetate and an aqueous ammonium chloride solution were added to the obtained residue, and the organic layer was further washed with an aqueous ammonium chloride solution and saturated brine in this order. The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 40) to obtain trans-1,2-bis (3-tert-amyl-5-tert-butyl-2- Hydroxybenzylsulfanyl) cyclooctane 1.5 g (yield> 99%) was obtained as a yellow oil.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.649 (t, J = 8 Hz, 6H), 1.1 ～ 2.0 (m, 46H), 2.64 (m, 2H), 3.81 (d, J = 13 Hz, 2H), 3.90 (d, J = 13 Hz, 2H ), 6.90 (d, J = 2 Hz, H2H), 7.19 (d, J = 2 Hz, 2H).
(Reference Example 18)
Synthesis of [cyclooctanediyl-trans-1,2-bis (3-tert-amyl-5-tert-butyl-2-oxoylbenzylsulfanyl)] dichlorohafnium
In a glove box under a nitrogen atmosphere, trans-1,2-bis (3-tert-amyl-5-tert-butyl-2-hydroxybenzylsulfanyl) cyclooctane 130 mg (0.20 ク mmol) of toluene (50 mL Schlenk tube) To a solution of 1 mL), a solution of dichloro {1,1′-oxybis [ethane] [bis (phenylmethyl) hafnium]} 100 μmg (0.20 mmol) in toluene (1 mL) was added dropwise at room temperature. After 1.5 hours, volatile components were distilled off under reduced pressure. The obtained residue was washed with pentane and dried under reduced pressure to give [cyclooctanediyl-trans-1,2-bis (3-tert-amyl-5-tert-butyl-2-oxoylbenzylsulfanyl) ] Dichlorohafnium-130 mg (yield 69%) was obtained as a white powder.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.702 (t, J = 7 Hz, 6H), 1.1 ～ 2.3 (m, 46H), 2.60 (brs, 2H), 3.87 (d, J = 14 Hz, 2H), 4.49 (d, J = 14 Hz, 2H ), 6.86 (d, J = 2 Hz, 2H), 7.33 (d, J = 2 Hz, 1H).
(Reference Example 19)
Synthesis of trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1-methyl-1-naphthylethyl) benzylsulfanyl] cyclooctane
(1) Synthesis of 4-tert-butyl-2- (1-methyl-1-naphthylethyl) phenol
4-tert-butylphenol 6.6 g (44 mmol), p-toluenesulfonic acid monohydrate 73 mg (0.38 mmol) and heptane 20 mL were added to nitrogen-substituted 50 mL Schlenk and heated to 100 ° C. A solution prepared by dissolving 3.7 g (22 mmol) of isopropenylnaphthalene in 5 mL of heptane was added dropwise thereto and stirred at room temperature for 1 hour. The reaction solution was poured into an aqueous sodium bicarbonate solution. After the organic layer was dried over anhydrous magnesium sulfate, the volatile component was distilled off under reduced pressure. The obtained white solid was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 10) to give 3.0 g of 4-tert-butyl-2- (1-methyl-1-naphthylethyl) phenol (yield). 43%) was obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.38 (s, 9H), 1.79 (s, 6H), 4.34 (s, 1H), 6.66 (d, J = 8 Hz, 1H), 7.19-7.30 (m, 2H), 7.44-7.54 (m, 3H) , 7.75 ～ 7.92 (m, 4H).
(2) Synthesis of 4-tert-butyl-2-hydroxymethyl-6- (1-methyl-1-naphthylethyl) phenol
In a 500 mL flask purged with nitrogen, 1.7 g (5.4 mmol) of 4-tert-butyl-2- (1-methyl-1-naphthylethyl) phenol, 2.0 g (20 mmol) of magnesium chloride, 0.9 g of paraformaldehyde (30 mmol) ) And 20 mL of tetrahydrofuran were added. To this was added 2.8 mL (20 mmol) of triethylamine, and the mixture was heated to reflux for 3 hours. The reaction solution was allowed to cool to room temperature, and the insoluble material was filtered off. After distilling off volatile components from the filtrate under reduced pressure, ethyl acetate and water were added to the residue. The organic layer was washed with 1M HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 4.0 g of a mixture containing 5-tert-butyl-3- (1-methyl-1-naphthylethyl) salicylaldehyde (yield 73%).
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.37 (s, 9H), 1.83 (s, 6H), 4.34 (s, 1H), 7.2 to 7.9 (m, 9H), 9.82 (s, 1H), 11.2 (s, 1H).
To the 200 mL flask purged with nitrogen, 1.4 g of the above mixture, 10 mL of tetrahydrofuran, and 10 mL of methanol were added. To this was slowly added 160 （mg (4.2 mmol) of sodium borohydride, and the mixture was warmed to room temperature and stirred for 1 hour. After distilling off volatile components from the reaction solution under reduced pressure, water and ethyl acetate were added. The organic layer was washed with 1M HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, the obtained colorless oil was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 10 to 1: 3) to give 4-tert-butyl-2- Hydroxymethyl-6- (1-methyl-1-naphthylethyl) phenol 1.3 g (yield 91%) was obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.37 (s, 9H), 1.80 (s, 6H), 2.08 (t, J = 6 Hz, 1H), 4.62 (d, J = 6 Hz, 2H), 5.60 (s, 1H), 7.1-7.9 (m , 9H).
(3) Synthesis of tert-butyl-2-hydroxy-3- (1-methyl-1-naphthylethyl) benzyl bromide
To a 500 mL flask purged with nitrogen, 1.3 g (3.6 mmol) of 4-tert-butyl-2-hydroxymethyl-6- (1-methyl-1-naphthylethyl) phenol and 10 mL of dichloromethane were added. To this, 2.7 mL of phosphorus tribromide (1.0 M M dichloromethane solution, 2.7 mmol) was added and stirred at room temperature for 2 hours. Water was added to the reaction solution, and the organic layer was further washed twice with water and then with saturated brine. After drying the organic layer over anhydrous magnesium sulfate, the volatile components are distilled off under reduced pressure to give 1.5 g of tert-butyl-2-hydroxy-3- (1-methyl-1-naphthylethyl) benzyl bromide. (Yield> 99%) was obtained as a pale yellow oil.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.30 mm (s, 9H), 1.79 mm (s, 6H), 4.43 mm (s, 2H), 7.2-8.0 mm (m, 9H).
(4) Synthesis of trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1-methyl-1-naphthylethyl) benzylsulfanyl] cyclooctane
In a 50-mL flask purged with nitrogen, add 1.1 g (2.5 mmol) 5-tert-butyl-2-hydroxy-3- (1-methyl-1-naphthylethyl) benzyl bromide, trans-cyclooctane-1,2-dithiol 0.18 g (1.0 mmol) and 7 mL of tetrahydrofuran were added and ice-cooled. Triethylamine 0.70 mL (5.1 mmol) was added thereto, and the mixture was stirred at 0 ° C for 1 hour and at room temperature for 2 hours. Volatile components were distilled off under reduced pressure, and ethyl acetate and an aqueous ammonium chloride solution were added to the resulting residue. The organic layer was further washed with an aqueous ammonium chloride solution and saturated brine in that order, and then dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, it was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 10) to obtain trans-1,2-bis [5-tert-butyl-2-hydroxy -3- (1-Methyl-1-naphthylethyl) benzylsulfanyl] cyclooctane (0.9 g, yield:> 99%) was obtained as a pale yellow solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.8 ~ 1.8 (m, 42H), 2.46 (m, 2H), 2.51 (m, 4H), 3.51 (m, 4H), 5.72 (s, 2H), 6.99 (d, J = 2 Hz, 2H), 7.20 ~ 7.23mm (m, 2H), 7.35 ~ 7.44mm (m, 6H), 7.60 ~ 7.89mm (m, 8H).
(Reference Example 20)
Synthesis of {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (1-methyl-1-naphthylethyl) benzylsulfanyl]} dichlorohafnium
Trans-1,2-bis (5-tert-butyl-2-hydroxy-3- (1-methyl-1-naphthylethyl) benzylsulfanyl) cyclooctane 170 mg in a 50 グローブ mL Schlenk tube in a glove box under nitrogen atmosphere To a solution of (0.20 トルエン mmol) in toluene (1 mL), dichloro {1,1'-oxybis [ethane] [bis (phenylmethyl) hafnium]} 100 mg (0.20 mmol) in toluene (1 mL) is added dropwise at room temperature did. After 1.5 hours, volatile components were distilled off under reduced pressure. The obtained residue was washed with pentane and dried under reduced pressure to give {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (1-methyl-1- Naphthylethyl) benzylsulfanyl]} dichlorohafnium 110 mg (yield 51%) was obtained as a white powder.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.50 ~ 2.2 (m, 56H), 2.48 (d, J = 14 Hz, 2H), 3.28 (d, J = 14 Hz, 2H), 6.58 (s, 2H), 6.97 (d, J = 8 Hz, 2H ), 7.3-7.5 (m, 6H), 7.59 (s, 2H), 7.68 (d, J = 6 Hz, 2H), 7.84 (d, J = 7 Hz, 2H), 8.10 (s, 2H).
(Reference Example 21)
Synthesis of trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1-methylcyclohexyl) benzylsulfanyl] cyclooctane
(1) Synthesis of 4-tert-butyl-2- (1-methylcyclohexyl) phenol
4-tert-butylphenol 3.3 g (22 mmol), 1-methylcyclohexanol 2.7 mL (22 mmol) and dichloromethane 20 mL were added to nitrogen-substituted 50 mL Schlenk, and cooled to 0 ° C. in an ice bath. To this was added 1.2 mL (22 mmol) of sulfuric acid and stirred at room temperature for 20 minutes. The reaction solution was poured into an aqueous sodium bicarbonate solution. After the organic layer was dried over anhydrous magnesium sulfate, the volatile component was distilled off under reduced pressure. The obtained white solid was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 10) to give 3.8 g of 4-tert-butyl-2- (1-methylcyclohexyl) phenol (yield 70%) Was obtained as a colorless oil.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.2 ~ 1.8 (m, 20H), 2.19 (m, 2H), 4.60 (s, 1H), 6.58 (d, J = 8 Hz, 1H), 7.06 (dd, J = 2 Hz, 8 Hz, 1H), 7.31 (d, J = 2 Hz, 1H).
(2) Synthesis of 4-tert-butyl-2-hydroxymethyl-6- (1-methylcyclohexyl) phenol
In a 200 mL four-necked flask purged with nitrogen, 4-tert-butyl-2- (1-methylcyclohexyl) phenol 3.8 g (16 mmol), magnesium chloride 3.0 g (31 mmol), paraformaldehyde 2.3 g (78 mmol) and tetrahydrofuran 70 mL was added. Triethylamine 4.3 mL (31 mmol) was added thereto and heated to reflux for 3 hours. The reaction solution was allowed to cool to room temperature, and the insoluble material was filtered off. After distilling off volatile components from the filtrate under reduced pressure, ethyl acetate and water were added to the residue. The organic layer was washed with 1M HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 4.0 g of a mixture containing 5-tert-butyl-3- (1-methylcyclohexyl) salicylaldehyde (yield 91%).
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.2 ~ 1.8 (m, 20H), 2.20 (m, 2H), 7.33 (d, J = 2 Hz, 1H), 7.61 (d, J = 2 Hz, 1H), 9.86 (s, 1H), 11.7 (s , 1H).
To a 200 mL four-necked flask purged with nitrogen, 4.0 g of the above mixture, 40 mL of tetrahydrofuran, and 20 mL of methanol were added and ice-cooled. To this was slowly added sodium borohydride 330 mg (8.7 mmol), and the mixture was warmed to room temperature and stirred for 15 hours. After distilling off volatile components from the reaction solution under reduced pressure, water and ethyl acetate were added. The organic layer was washed with 1M HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, the obtained colorless oil was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 9) to give 4-tert-butyl-2-hydroxymethyl-6 2.4 g of (1-methylcyclohexyl) phenol (yield 61%) was obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.2 ~ 1.8 (m, 20H), 2.16 (brs, 1H), 2.19 (m, 2H), 4.84 (s, 2H), 6.88 (d, J = 2 Hz, 1H), 7.30 (d, J = 2 Hz , 1H), 7.52 (s, 1H).
(3) Synthesis of tert-butyl-2-hydroxy-3- (1-methylcyclohexyl) benzyl bromide
4-tert-Butyl-2-hydroxymethyl-6- (1-methylcyclohexyl) phenol (2.4 g, 8.8 mmol) and dichloromethane (40 ml) were added to a nitrogen-substituted 200 mL four-necked flask. To this, phosphorus tribromide (5.3 mL, 1.0 M dichloromethane solution, 5.3 mmol) was added and stirred at room temperature for 3.5 hours. Water was added to the reaction solution, and the organic layer was further washed twice with water and then with saturated brine. After drying the organic layer with anhydrous magnesium sulfate, the volatile component was distilled off under reduced pressure to give 3.8 g of tert-butyl-2-hydroxy-3- (1-methylcyclohexyl) benzyl bromide (yield> 99%) was obtained as a pale yellow oil.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.2 ~ 1.8 (m, 20H), 2.18 (m, 2H), 4.58 (s, 2H), 7.08 (d, J = 2 Hz, 1H), 7.35 (d, J = 2 Hz, 1H).
(4) Synthesis of trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1-methylcyclohexyl) benzylsulfanyl] cyclooctane
In a 50-mL four-necked flask purged with nitrogen, tert5-tert-butyl-2-hydroxy-3- (1-methylcyclohexyl) benzyl bromide 1.5 g (4.3 mmol), trans-cyclooctane-1,2-dithiol 0.38 g (2.1 mmol) and 22 mL of tetrahydrofuran were added and ice-cooled. To this, 0.90 エチル mL (6.5 mmol) of triethylamine was added and stirred at room temperature for 22.5 hours. The reaction solution was filtered, and volatile components were distilled off from the filtrate under reduced pressure. Ethyl acetate and aqueous ammonium chloride solution were added to the resulting residue. The organic layer was further washed with an aqueous ammonium chloride solution and saturated brine in that order, and then dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, it was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 20) to obtain trans-1,2-bis [5-tert-butyl-2-hydroxy 7 of 3- (1-methylcyclohexyl) benzylsulfanyl] cyclooctane and trans-1- [5-tert-butyl-2-hydroxy-3- (1-methylcyclohexyl) benzylsulfanyl] -2-sulfanylcyclooctane 1: 1.6 g of mixture was obtained. This mixture and 0.18 g (0.53 mmol) of tert5-tert-butyl-2-hydroxy-3- (1-methylcyclohexyl) benzyl bromide were dissolved in 20 mL of tetrahydrofuran and cooled on ice. To this, 0.10 mL (0.72 mmol) of triethylamine was added and stirred for 22 hours. The reaction solution was filtered, and volatile components were distilled off from the filtrate under reduced pressure. Ethyl acetate and an aqueous ammonium chloride solution were added to the obtained residue, and the organic layer was further washed with an aqueous ammonium chloride solution and saturated brine in this order. The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 20), whereby trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1 -Methylcyclohexyl) benzylsulfanyl] cyclooctane 1.6 g (yield 99%) was obtained as a yellow oil.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.1 ~ 1.8 (m, 50H), 1.90 (m, 2H), 2.20 (m, 4H), 2.64 (m, 2H), 3.80 (d, J = 13 Hz, 2H), 3.89 (d, J = 13 Hz , 2H), 6.90 (d, J = 2 Hz, 2H), 7.27 (d, J = 2 Hz, 2H).
(Reference Example 22)
Synthesis of {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (1-methylcyclohexyl) benzylsulfanyl]} dichlorohafnium
Trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1-methylcyclohexyl) benzylsulfanyl] cyclooctane 140 mg (0.20 mmol) in a 50 （mL Schlenk tube in a glove box under nitrogen atmosphere Toluene (1 mL) solution of dichloro {1,1'-oxybis [ethane] [bis (phenylmethyl) hafnium]} 100 mg (0.20 mmol) in toluene (1 mL) was added dropwise at room temperature. After 1.5 hours, volatile components were distilled off under reduced pressure. The residue obtained was washed with pentane and dried under reduced pressure to give {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (1-methylcyclohexyl) benzyl Sulfanyl]} dichlorohafnium-130 mg (yield 69%) was obtained as a white powder.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.8 ~ 2.4 (m, 56H), 2.58 (brs, 2H), 3.86 (d, J = 14 Hz, 2H), 4.48 (d, J = 14 Hz, 2H), 6.85 (s 2H), 7.41 (s, 2H).
(Reference Example 23)
Synthesis of trans-1,2-bis [5-tert-butyl-3- (2, 3-dimethyl-2-butyl) -2-hydroxybenzylsulfanyl] cyclooctane
(1) Synthesis of 4-tert-butyl-2- (2, 3-dimethyl-2-butyl) phenol
To 50 置換 mL Schlenk purged with nitrogen, 3.3 g (22 mmol) of 4-tert-butylphenol, 2.7 mL (22 mmol) of 2, 3-dimethyl-2-butanol and 20 mL of dichloromethane were added and cooled to 0 ° C in an ice bath. . To this was added 1.2 mL (22 mmol) of sulfuric acid and stirred at room temperature for 20 minutes. The reaction solution was poured into an aqueous sodium bicarbonate solution. After the organic layer was dried over anhydrous magnesium sulfate, the volatile component was distilled off under reduced pressure. The obtained white solid was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 10) to give 4.4 g of 4-tert-butyl-2- (2, 3-dimethyl-2-butyl) phenol ( Yield 86%) was obtained as a colorless oil.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.746 (d, J = 7 Hz, 6H), 1.27 (s, 9H), 1.32 (s, 6H), 2.72 (m, J = 8 Hz, 1H), 4.61 (s, 1H), 6.56 (d, J = 8 Hz, 1H), 7.05 (dd, J = 2 Hz, 8 Hz, 1H), 7.23 (d, J = 2 Hz, 1H).
(2) Synthesis of 4-tert-butyl-6- (2, 3-dimethyl-2-butyl) -2-hydroxymethylphenol
In a 300 mL four-necked flask purged with nitrogen, 4.4 g (19 mmol) of 4-tert-butyl-2- (2, 3-dimethyl-2-butyl) phenol, 3.6 g (38 mmol) of magnesium chloride, 2.9 g of paraformaldehyde (95 mmol) and 85 mL of tetrahydrofuran were added. Triethylamine 5.3 mL (38 mL) was added thereto, and the mixture was heated to reflux for 2 hours. The reaction solution was allowed to cool to room temperature, and the insoluble material was filtered off. After distilling off volatile components from the filtrate under reduced pressure, ethyl acetate and water were added to the residue. The organic layer was washed with 1M HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 4.8 g of a mixture containing 5-tert-butyl-3- (2, 3-dimethyl-2-butyl) salicylaldehyde (yield 96%).
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.748 (d, J = 7 Hz, 6H), 1.28 (s, 9H), 1.33 (s, 6H), 2.72 (m, J = 7 Hz, 2H), 7.33 (d, J = 2 Hz, 1H), 7.54 (d, J = 2 Hz, 1H), 9.86 (s, s1H), 11.7 (s, 1H).
4.8 g of the above mixture, 50 ml of tetrahydrofuran and 25 ml of methanol were added to a 200 ml four-necked flask purged with nitrogen, and ice-cooled. To this was slowly added 420 ホウ素 mg (11 mmol) of sodium borohydride, and the mixture was warmed to room temperature and stirred for 15 hours. After distilling off volatile components from the reaction solution under reduced pressure, water and ethyl acetate were added. The organic layer was washed with 1M HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, the obtained colorless oil was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 20 to 1: 9) to give 4-tert-butyl-6- 2.9 g (yield 60%) of (2, 3-dimethyl-2-butyl) -2-hydroxymethylphenol was obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.755 (d, J = 7 Hz, 3H), 1.28 (s, 9H), 1.33 (s, 6H), 2.06 (s, 1H), 2.68 (m, J = 7 Hz, 1H), 4.83 (s, 2H ), 6.87 (d, J = 2 Hz, H1H), 7.22 (d, J = 2 Hz, 1H), 7.48 (s, 1H).
(3) Synthesis of 5-tert-butyl-3- (2, 3-dimethyl-2-butyl) -2-hydroxybenzyl bromide
4-tert-butyl-6- (2, 3-dimethyl-2-butyl) -2-hydroxymethylphenol 2.9 g (11 mmol) and dichloromethane 50 ジクロロメタン mL were added to a nitrogen-substituted 200 mL four-necked flask. To this was added 6.6 mL of phosphorus tribromide (1.0 M dichloromethane solution, 6.6 mmol), and the mixture was stirred at room temperature for 3.5 hours. Water was added to the reaction solution, and the organic layer was further washed twice with water and then with saturated brine. After drying the organic layer with anhydrous magnesium sulfate, the volatile component was distilled off under reduced pressure to give 5-tert-butyl-3- (2, 3-dimethyl-2-butyl) -2-hydroxybenzyl bromide 3.7. g (yield> 99%) was obtained as a pale yellow oil.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.759 (d, J = 7 Hz, 3H), 1.28 (s, 9H), 1.34 (s, 6H), 2.56 (m, J = 7 Hz, 1H), 4.58 (s, 2H), 7.08 (d, J = 2 Hz, 1H), 7.27 (d, J = 2 Hz, 1H).
(4) Synthesis of trans-1,2-bis [5-tert-butyl-3- (2, 3-dimethyl-2-butyl) -2-hydroxybenzylsulfanyl] cyclooctane
In a 50-mL four-necked flask purged with nitrogen, 1.5 g (4.6 mmol) of 5-tert-butyl-3- (2, 3-dimethyl-2-butyl) -2-hydroxybenzyl bromide, trans-cyclooctane-1, 2-Dithiol 0.40 g (2.2 mmol) and tetrahydrofuran 24 mL were added and ice-cooled. Triethylamine 1.0 mL (7.2 mmol) was added thereto and stirred at room temperature for 22 hours. The reaction solution was filtered, and volatile components were distilled off from the filtrate under reduced pressure. Ethyl acetate and aqueous ammonium chloride solution were added to the resulting residue. The organic layer was further washed with an aqueous ammonium chloride solution and saturated brine in that order, and then dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, the product was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 40-1: 20) to obtain trans-1,2-bis [5-tert-butyl -3- (2, 3-dimethyl-2-butyl) -2-hydroxybenzylsulfanyl] cyclooctane 1.7 g (yield> 99%) was obtained as a yellow oil.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.734 (d, J = 7 Hz, 12H), 1.1-1.7 (m, 40H), 1.89 (m, 2H), 2.62 (m, 2H), 2.72 (m, J = 7 Hz, 2H), 3.61 (d , J = 13 Hz, 2H), 3.89 (d, J = 13 Hz, 2H), 6.89 (d, J = 2 Hz, 2H), 7.20 (d, J = 2 Hz, 2H).
(Reference Example 24)
Synthesis of {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (2, 3-dimethyl-2-butyl) -2-oxoylbenzylsulfanyl]} dichlorohafnium
Trans-1,2-bis (5-tert-butyl-3- (2, 3-dimethyl-2-butyl) -2-hydroxybenzylsulfanyl) cyclooctane 130 in a 50 mL Schlenk tube in a glove box under nitrogen atmosphere To a solution of mg (0.20 の mmol) in toluene (1 mL), add a solution of dichloro {1,1'-oxybis [ethane] [bis (phenylmethyl) hafnium]} 100 mg (0.20 mmol) in toluene (1 mL) at room temperature. It was dripped. After 1.5 hours, volatile components were distilled off under reduced pressure. The obtained residue was washed with pentane and dried under reduced pressure to obtain {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (2, 3-dimethyl-2-butyl) 2-Oxoylbenzylsulfanyl]} dichlorohafnium-> 30 mg mg (yield: 16%) was obtained as a white powder.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.719 (d, J = 6 Hz, 6H), 0.80 ~ 1.9 (m, 48H), 2.57 (brs, 2H), 3.06 (m, J = 6 Hz, 2H), 3.87 (d, J = 14 Hz, 2H ), 4.48 (d, J = 14 Hz, 2H), 6.85 (d, J = 2 Hz, 2H), 7.34 (d, J = 2 Hz, 2H).
(Reference Example 25)
Synthesis of trans-1,2-bis (2-hydroxy-3-trimethylsilyl-5-methylbenzylsulfanyl) cyclooctane
(1) Synthesis of 3-trimethylsilyl-5-methyl-2-hydroxybenzyl alcohol
2-Hydroxo-5-methyl-3- トリメチル (trimethylsilyl) benzaldehyde 9.57 g (45.9 mmol) was dissolved in 70 mL of diethyl ether and cooled to 0 ° C. Thereto was added 2.27 g (59.8 mmol) of lithium aluminum hydride, and the mixture was stirred at 0 ° C for 2 hours. Dilute hydrochloric acid and diethyl ether were added, and the ether layer was washed with water and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to give 9.57 g of 3-trimethylsilyl-5-methyl-2-hydroxybenzyl alcohol as colorless crystals. Rate 98%).
¹H NMR (500 MHz, δ, ppm, CDCl_Three)
0.30 (s, 9H), 2.03 (br s, 1H), 2.25 (s, 3H), 4.83 (br s, 1H), 6.84 (d, J = 2 Hz, 1H), 7.11 (d, J = 2 Hz , 1H), 7.39 (s, 1H).
(2) Synthesis of trans-1,2-bis (2-hydroxy-3-trimethylsilyl-5-methylbenzylsulfanyl) cyclooctane
In an argon atmosphere, 1.03 g (4.87 mmol) of 3-trimethylsilyl-5-methyl-2-hydroxybenzyl alcohol was dissolved in 30 ml of diethyl ether and cooled to 0 ° C. 1,8-diazabicyclo [5.4.0] undec-7-ene 6.2 エン mL (44.5 mmol) was added thereto, and then phosphorus tribromide 0.35 mL (3.69 mmol) was added, followed by stirring at 25 ° C for 2 hours. Thereto, a solution obtained by dissolving 289.2 mg (1.64 mmol) of trans-cyclooctane-1,2-dithiol (document known) in 20 mL of diethyl ether was transferred in a tube under an argon atmosphere, and stirred for 13 hours while heating under reflux. A dilute aqueous ammonium chloride solution and diethyl ether were added, and the ether layer was washed with water and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: dichloromethane), and trans-1,2-bis (2-hydroxy-3-trimethylsilyl-5-methylbenzylsulfanyl) cyclooctane 672.9 mg (yield as a colorless oil) 73%).
¹H NMR (500 MHz, δ, ppm, CDCl_Three)
0.29 (s, 18H), 1.15-1.96. (M, 12H), 2.25 (s, 6H), 2.65 (br s, 2H), 3.73-3.85 (m, 4H), 6.85 (d, J = 2 Hz, 2H ), 6.90 (s, 2H), 7.10 (d, J = 2 Hz, 2H).
¹³C NMR (125.7 MHz, δ, ppm, CDCl₃₎
-0.88, 20.5, 25.7, 26.0, 30.9, 34.5, 49.9, 120.8, 127.7, 129.1, 132.4, 135.2, 158.4.
(Reference Example 26)
Synthesis of {cyclooctanediyl-trans-1,2-bis [2-oxoyl-3-trimethylsilyl-5-methylbenzylsulfanyl]} dichlorohafnium
In a glove box under nitrogen atmosphere, in a 50 mL Schlenk tube, trans-1,2-bis (2-hydroxy-3-trimethylsilyl-5-methylbenzylsulfanyl) cyclooctane 300mg (0.53mmol) in toluene (5 mL) solution Dichloro {1,1′-oxybis [ethane] [bis (phenylmethyl) hafnium]} 0.27 g (0.53 mmol) in toluene (5 mL) was added dropwise at room temperature. After 1.5 hours, the reaction solution was filtered, and volatile components were distilled off from the filtrate under reduced pressure. The obtained residue was washed with pentane and dried under reduced pressure to give 300 シクロ mg of {cyclooctanediyl-trans-1,2-bis [2-oxoyl-3-trimethylsilyl-5-methylbenzylsulfanyl]} dichlorohafnium ( (Yield 69%) Obtained as a white powder.
¹H NMR (500 MHz, δ, ppm, CDCl_Three)
0.425 (s, 18H), 0.70 ~ 2.0 ～ (m, 12H), 2.27 (s, 6H), 2.63 (brs, 2H), 3.82 (d, J = 14 Hz, 2H), 4.42 (d, J = 14 Hz , 2H), 6.83 (s, 2H), 7.23 (s, 1H).
(Reference Example 27)
Synthesis of [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl)] dichlorohafnium
In a glove box under a nitrogen atmosphere, trans-1,2-bis (5-tert-butyl-2-hydroxy-3-triphenylmethylbenzylsulfanyl) cyclooctane 0.40 g (0.41 mmol) of toluene (50 mL Schlenk tube) To a 4 mL solution, a solution of dichloro {1,1′-oxybis [ethane] [bis (phenylmethyl) hafnium]} 0.21 g (0.41 mmol) in toluene (4 mL) was added dropwise at room temperature. After 6 hours, the reaction solution was filtered, and volatile components were distilled off from the filtrate under reduced pressure. The obtained residue was washed with hexane and then dissolved in a mixed solvent of diethyl ether / hexane. After concentration under reduced pressure, hexane was added and the mixture was allowed to stand at room temperature for 3 days. The precipitated solid was collected and dried under reduced pressure to obtain [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-2-oxoyl-3-triphenylmethylbenzylsulfanyl)] dichlorohafnium 0.31 g (yield 62%) was obtained as a white powder.
₁H NMR (500 MHz, δ, ppm, CDCl_Three)
0.50-1.6 (m, 30H), 1.83 (brs, 2H), 3.44 (d, J = 14 Hz, 2H), 3.98 (d, J = 14 Hz, 2H), 6.7-7.4 (m, 34H).
(Reference Example 28)
Synthesis of trans-1,2-bis [5-bromo-3- (1-adamantyl) -2-hydroxybenzylsulfanyl] cyclooctane
(1) Synthesis of 4-bromo-2- (1-adamantyl) phenol
4-Bromo-2- (1-adamantyl) anisole 16 g (50 mmol) and dichloromethane 300 mL were added to a nitrogen-substituted 1000 mL four-necked flask and cooled to -63 ° C. To this was added 100 mL of phosphorus tribromide (1.0 M dichloromethane solution, 100 加え mmol), and the mixture was stirred at room temperature for 10 minutes. After raising the temperature to room temperature, it was poured into 400 g of ice water. The organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate. After drying over anhydrous magnesium sulfate, volatile components were distilled off under reduced pressure. The resulting white solid was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 40 to 1: 3) to give 13 g of 4-bromo-2- (1-adamantyl) phenol (yield 88%) ) Was obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.77 (s, 6H), 2.08 (s, 9H), 4.81 (s, 1H), 6.53 (d, J = 8 Hz, 1H), 7.15 (dd, J = 2 Hz, 8 Hz, 1H), 7.29 ( d, J = 2 Hz, 1H).
(2) Synthesis of 4-bromo-6- (1-adamantyl) -2-hydroxymethylphenol
In a nitrogen-substituted 500 mL four-necked flask, 11 g (37 mmol) of 4-bromo-2- (1-adamantyl) phenol, 7.1 g (74 mmol) of magnesium chloride, 5.5 g (180 mmol) of paraformaldehyde and 230 mL of tetrahydrofuran Was added. To this was added 11 mL (79 mL) of triethylamine, and the mixture was heated to reflux for 2 hours. The reaction solution was allowed to cool to room temperature, and the insoluble material was filtered off. After distilling off volatile components from the filtrate under reduced pressure, ethyl acetate and water were added to the residue. The organic layer was washed with 1M HCl, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 12 g of a mixture containing 5-bromo-3- (1-adamantyl) salicylaldehyde (99% yield).
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.78 (s, 6H), 2.08 (s, 3H), 2.10 (s, 6H), 4.81 (s, 1H), 6.53 (d, J = 8 Hz, 1H), 7.51 (m, 2H), 9.80 (s , 1H), 11.8 (s, 1H).
To a 300-mL four-necked flask purged with nitrogen, 13 mL of the above mixture, 150 mL of tetrahydrofuran, and 55 mL of methanol were added and cooled on ice. To this was slowly added 900 mg (24 mmol) of sodium borohydride, and the mixture was warmed to room temperature and stirred for 20 hours. After distilling off volatile components from the reaction solution under reduced pressure, water and ethyl acetate were added. The extract was washed with saturated brine and dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, the obtained colorless oil was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 20 to 1: 2) to give 4-bromo-6- (1 -Adamantyl) -2-hydroxymethylphenol 9.8 g (yield 74%) was obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, DMSO-d6)
1.78 (s, 6H), 2.03 (s, 3H), 2.10 (s, 6H), 4.58 (s, 2H), 7.07 (d, J = 3 Hz, 1H), 7.22 (d, J = 3 Hz, 1H ).
(3) Synthesis of 5-bromo-3- (1-adamantyl) -2-hydroxybenzyl bromide
4-Bromo-6- (1-adamantyl) -2-hydroxymethylphenol 9.8 g (29 mmol) and dichloromethane 180 mL were added to a nitrogen-substituted 300 mL 4-neck flask. A mixed solution (17 mmol) of dichloromethane (8 ジクロロメタン mL) and phosphorus tribromide (1.8 mL) was added thereto and stirred at room temperature for 3.5 hours. The reaction solution was added to ice water, and the organic layer was washed twice with saturated brine. After drying the organic layer over anhydrous magnesium sulfate, the volatile components were distilled off under reduced pressure to obtain 12 g of 5-bromo-3- (1-adamantyl) -2-hydroxybenzyl bromide (> 99% yield). Obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.78 (s, 6H), 2.09 (s, 9H), 4.47 (s, 2H), 7.24 (d, J = 2 Hz, 1H), 7.32 (d, J = 2 Hz, 1H).
(4) Synthesis of trans-1,2-bis [5-bromo-3- (1-adamantyl) -2-hydroxybenzylsulfanyl] cyclooctane
In a 100 mL 4-neck flask with nitrogen substitution, 5-bromo-3- (1-adamantyl) -2-hydroxybenzyl 1.4 g (3.4 mmol), trans-cyclooctane-1,2-dithiol 0.28 g (1.6 mmol) ) And 22 mL of tetrahydrofuran were added and cooled on ice. Triethylamine トリ 0.70 mL (5.0 mmol) was added thereto and stirred at room temperature for 14.5 hours. The reaction solution was filtered, and volatile components were distilled off from the filtrate under reduced pressure. Ethyl acetate and aqueous ammonium chloride solution were added to the resulting residue. The organic layer was further washed with an aqueous ammonium chloride solution and saturated brine in that order, and then dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, the product was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 40-1: 20), whereby trans-1,2-bis [5-bromo-2 8: 1 of 2-hydroxy-3- (1-adamantyl) benzylsulfanyl] cyclooctane with trans-1- [5-bromo-2-hydroxy-3- (1-adamantyl) benzylsulfanyl] -2-sulfanylcyclooctane 1.3 g of mixture was obtained. This mixture and 0.14 g (0.53 mmol) of 5-bromo-2-hydroxy-3- (1-adamantyl) benzyl bromide were dissolved in 22 mL of tetrahydrofuran and cooled on ice. To this, 0.06 mL (0.43 mmol) of triethylamine was added and stirred for 22 hours. The reaction solution was filtered, and volatile components were distilled off from the filtrate under reduced pressure. Ethyl acetate and an aqueous ammonium chloride solution were added to the obtained residue, and the organic layer was further washed with an aqueous ammonium chloride solution and saturated brine in this order. The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 20 to 1: 5) to obtain trans-1,2-bis (5-bromo-2-hydroxy-3- (1-adamantyl) benzylsulfanyl) cyclooctane 1.4 g (yield> 99%) was obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.2 ~ 2.0 (m, 24H), 2.05 (s, 6H), 2.10 (s, 12H), 2.61 (m, 2H), 3.73 (d, J = 14 Hz, 2H), 3.82 (d, J = 14 Hz , 2H), 7.04 (d, J = 2 Hz, 2H), 7.07 (s, 2H), 7.27 (d, J = 2 Hz, 2H).
(Reference Example 29)
Synthesis of {cyclooctanediyl-trans-1,2-bis [5-bromo-2-oxoyl-3- (1-adamantyl) benzylsulfanyl]} dichlorohafnium
In a glove box under a nitrogen atmosphere, trans-1,2-bis [5-bromo-2-hydroxy-3- (1-adamantyl) benzylsulfanyl] cyclooctane 160 mg (0.20 mmol) of toluene (50 mL Schlenk tube) To a solution of 1 mL), a solution of dichloro {1,1′-oxybis [ethane] [bis (phenylmethyl) hafnium]} 100 μmg (0.20 mmol) in toluene (1 mL) was added dropwise at room temperature. After stirring for 1 hour, volatile components were distilled off under reduced pressure. The obtained residue was washed with pentane and dried under reduced pressure to obtain {cyclooctanediyl-trans-1,2-bis [5-bromo-2-oxoyl-3- (1-adamantyl) benzylsulfanyl]} Dichlorohafnium 62 mg mg (yield 29%) was obtained as a white powder.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.853 (m, 2H), 1.15 (m, 2H), 1.4 ~ 2.4 (m, 38H), 2.61 (brs, 2H), 3.82 (d, J = 14 Hz, 2H), 4.48 (d, J = 14 Hz , 2H), 7.02 (d, J = 2 Hz, 2H), 7.44 (d, J = 2 Hz, 2H).
(Reference Example 30)
Synthesis of trans-1,2-bis [2-hydroxy-3- (triisopropylsilyl) -5-methylbenzylsulfanyl] cyclooctane
(1) Synthesis of 3- (triisopropylsilyl) -5-methyl-2-hydroxybenzyl alcohol
2-hydroxy-5-methyl-3- (triisopropylsilyl) benzaldehyde (literature known) 1.38 g (4.71 mmol) was dissolved in 20 mL of diethyl ether and cooled to 0 ° C. Thereto was added lithium aluminum hydride 232.3 mg (6.12 mmol), followed by stirring at 0 ° C for 21 hours. Dilute hydrochloric acid and diethyl ether were added, the ether layer was washed with water and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to quantitatively obtain the title compound (1.41 g, including a small amount of solvent) as colorless crystals.
¹H NMR (500 MHz, δ, ppm, CDCl_Three)
1.09 (d, J = 8 Hz, 18H), 1.50 (sept, J = 8 Hz, 3H), 2.02 (br s, 1H), 2.26 (s, 3H), 4.81 (d, J = 5 Hz, 1H) , 6.84 (d, J = 2 Hz,) 1H), 7.14 (d, J = 2 Hz, 1H), 7.34 (s, 1H).
¹³C NMR (125.7 MHz, δ, ppm, CDCl_Three)
11.9, 19.1, 20.8, 65.5, 122.3, 123.4, 128.2, 129.7, 137.6, 159.7.
(2) Synthesis of trans-1,2-bis [2-hydroxy-3- (triisopropylsilyl) -5-methylbenzylsulfanyl] cyclooctane
In an argon atmosphere, 1.01 g (3.42 mmol) of 3- (triisopropylsilyl) -5-methyl-2-hydroxybenzyl alcohol was dissolved in 10 ml of tetrahydrofuran and cooled to 0 ° C. Thereto was added 0.8 mL (5.74 mmol) of triethylamine, 0.26 mL (3.35 mmol) of methanesulfonyl chloride was added, and the mixture was stirred at 25 ° C for 21 hours. Thereto, a solution obtained by dissolving 201.7 mg (1.14 mmol) of trans-cyclooctane-1,2-dithiol (document known) in 10 mL of tetrahydrofuran was transferred in a tube under an argon atmosphere, and stirred for 20 hours while heating under reflux. A saturated aqueous ammonium chloride solution and diethyl ether were added, the ether layer was washed with water and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: dichloromethane) to quantitatively obtain the title compound (1.01 g, containing a small amount of solvent) as a pale yellow oil.
¹H NMR (500 MHz, δ, ppm, CDCl_Three)
1.12 (d, J = 8 Hz, 36H), 1.16-2.00 (m, 12H), 1.51 (sept, J = Hz, 6H), 2.28 (s, 6H), 2.75 (br s, 2H), 3.77-3.88 (m, 4H), 6.79 (s, 2H), 6.89 (d, J = 2 Hz, 2H), 7.16 (d, J = 2 Hz, 2H).
¹³C NMR (125.7 MHz, δ, ppm, CDCl_Three)
11.9, 19.1, 19.2, 20.8, 25.9, 26.1, 31.3, 35.3, 50.3, 121.1, 123.2, 128.8, 132.3, 137.3, 158.8.
(Reference Example 31)
Synthesis of {cyclooctanediyl-trans-1,2-bis [2-oxoyl-3- (triisopropylsilyl) -5-methylbenzylsulfanyl]} dichlorohafnium
In a glove box under a nitrogen atmosphere, trans-1,2-bis [2-hydroxy-3- (triisopropylsilyl) -5-methylbenzylsulfanyl] cyclooctane 150 （mg (0.20 mmol) of toluene (50mL mL Schlenk tube) To a solution of 1 mL), a solution of dichloro {1,1′-oxybis [ethane] [bis (phenylmethyl) hafnium]} 100 μmg (0.20 mmol) in toluene (1 mL) was added dropwise at room temperature. After stirring for 1 hour, volatile components were distilled off under reduced pressure. The obtained residue was washed with pentane and dried under reduced pressure to obtain [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3- (triisopropylsilyl) -5-methylbenzylsulfanyl)] Dichlorohafnium 74 mg (yield 38%) was obtained as a white powder.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.80 ~ 2.0 (m, 54H), 2.36 (s, 6H), 2.70 (brs, 2H), 3.80 (d, J = 14 Hz, 2H), 4.41 (d, J = 14 Hz, 2H), 6.80 (s , 2H), 7.27 (s, 2H).
(Reference Example 32)
Synthesis of trans-1,2-bis [2-hydroxy-3- (tert-butyldimethylsilyl) -5-methylbenzylsulfanyl] cyclooctane
(1) Synthesis of 3- (tert-butyldimethylsilyl) -5-methyl-2-hydroxybenzyl alcohol
2-Hydroxy-5-methyl-3- (tert-butyldimethylsilyl) benzaldehyde (literature known) 6.64 g (25.0 mmol) was dissolved in 60 mL of diethyl ether and cooled to 0 ° C. Thereto was added lithium ion hydride 1.32 g (34.8 、 mmol), and the mixture was stirred at 0 ° C for 17 hours. Dilute hydrochloric acid and diethyl ether were added, and the ether layer was washed with water and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain 6.57 g (yield 98%) of the title compound as pale yellow crystals.
¹H NMR (500 MHz, δ, ppm, CDCl_Three)
0.31 (s, 6H), 0.91 (s, 9H), 2.03 (br s, 1H), 2.25 (s, 3H), 4.80 (d, J = 9 Hz, 1H), 6.85 (d, J = 3 Hz, 1H), 7.10 (d, J = 3 Hz, 1H), 7.27 (s, 1H).
(2) Synthesis of trans-1,2-bis [2-hydroxy-3- (tert-butyldimethylsilyl) -5-methylbenzylsulfanyl] cyclooctane
Under an argon atmosphere, 461.9 mg (1.72 mmol) of 3- (tert-butyldimethylsilyl) -5-methyl-2-hydroxybenzyl alcohol was dissolved in 5 mL of tetrahydrofuran and cooled to 0 ° C. To this was added 0.4 mL (2.87 mmol) of triethylamine, 0.13 mL (1.68 mmol) of methanesulfonyl chloride was added, and the mixture was stirred at 25 ° C. for 21 hours. A solution prepared by dissolving 104.2 mg (0.591 mmol) of trans-cyclooctane-1,2-dithiol (document known) in 5 mL of tetrahydrofuran was transferred into a tube under an argon atmosphere, and stirred for 20 hours under heating and reflux. A saturated aqueous ammonium chloride solution and diethyl ether were added, the ether layer was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: dichloromethane) to quantitatively obtain the title compound (424.4 mg, containing a small amount of solvent) as a pale yellow oil.
¹H NMR (500 MHz, δ, ppm, CDCl_Three)
0.30 (d, J = 4 Hz, 12H), 0.91 (s, 18H), 1.17-1.96 (m, 12H), 2.24 (s, 6H), 2.69 (br s, 2H), 3.73-3.85 (m, 4H ), 6.75 (s, 2H), 6.86 (d, J = 2 Hz, 2H), 7.09 (d, J = 2 Hz, 2H).
¹³C NMR (125.7 MHz, δ, ppm, CDCl_Three)
-4.39, -4.32, 17.8, 20.7, 25.9, 26.1, 27.3, 31.2, 35.0, 50.2, 121.2, 125.4, 128.9, 132.5, 136.9, 158.6.
(Reference Example 33)
Synthesis of {cyclooctanediyl-trans-1,2-bis [2-oxoyl-3- (tert-butyldimethylsilyl) -5-methylbenzylsulfanyl]} dichlorohafnium
In a glove box under a nitrogen atmosphere, trans-1,2-bis [2-hydroxy-3- (tert-butyldimethylsilyl) -5-methylbenzylsulfanyl] cyclooctane 150 mg (0.20 mmol) in a 50 mL Schlenk tube To a toluene (1 mL) solution, a toluene (1 mL) solution of dichloro {1,1'-oxybis [ethane] [bis (phenylmethyl) hafnium]} 100 mg (0.20 mmol) was added dropwise at room temperature. After stirring for 1 hour, volatile components were distilled off under reduced pressure. The residue obtained was washed with pentane and dried under reduced pressure to give {cyclooctanediyl-trans-1,2-bis [2-oxoyl-3- (tert-butyldimethylsilyl) -5-methylbenzylsulfanyl] ] Dichlorohafnium 10 mg mg (yield 6%) was obtained as a white powder.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.381 (s, 6H), 0.494 (s, 6H), 0.70-2.0 (m, 30H), 2.26 (s, 6H), 2.69 (br s, 2H), 3.81 (d, J = 14 Hz, 2H), 4.46 (d, J = 14 Hz, 2H), 6.82 (d, J = 2 Hz, 2H), 7.25 (d, J = 2 Hz, 2H).
(Reference Example 34)
Synthesis of trans-1,2-bis {5-tert-butyl-3- [1- (3,5-dimethylphenyl) -1-methylethyl] -2-hydroxybenzylsulfanyl} cyclooctane
(1) Synthesis of 1- (3,5-dimethylphenyl) -1-methylethanol
To a 200-mL four-necked flask purged with nitrogen, 60-mL of THF and 40-mL of 3,5-dimethylphenylmagnesium bromide (0.50-M THF solution, 20-mL mmol) were added. After cooling to −65 ° C., 5.2 mL (71 mmol) of acetone was added dropwise. The mixture was warmed to room temperature, stirred for 2.5 hours, and poured into 60 g of ice water. To this, 1M M HCl and diethyl ether were added. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. After drying over anhydrous magnesium sulfate, volatile components were distilled off under reduced pressure. The obtained pale yellow oil was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 10 to 1: 4), and then again purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 9). By purification, 1.7 g (yield 50%) of 1- (3,5-dimethylphenyl) -1-methylethanol was obtained as a pale yellow oil.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.56 (s, 6H), 1.76 (s, 1H), 2.33 (s, 6H), 6.89 (s, 1H), 7.10 (s, 2H).
(2) Synthesis of 4-tert-butyl-2- [1- (3,5-dimethylphenyl) -1-methylethyl] phenol
1- (3,5-dimethylphenyl) -1-methylethanol (1.7 g, 10 mmol), 4-tert-butylphenol (3.0 g, 20 タン mmol), and heptane (40 mL) were added to a nitrogen-substituted 100 mL flask. To this was added 40 mg (0.23 mmol) of p-toluenesulfonic acid, the temperature was raised to 100 ° C., and the mixture was stirred for 16 hours. After the reaction solution was cooled to room temperature, water and ethyl acetate were added. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate, and then the volatile component was distilled off under reduced pressure. The resulting light orange solid was purified by silica gel column chromatography (developing solvent, ethyl acetate: hexane = 1: 20), and then purified again by silica gel column chromatography (developing solvent, ethyl acetate: hexane = 1: 50). Then, 1.9 g of 4-tert-butyl-2- [1- (3,5-dimethylphenyl) -1-methylethyl] phenol (yield: 66%) was obtained as a colorless oil.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.36 (s, 9H), 1.65 (s, 6H), 2.28 (s, 6H), 4.38 (s, 1H), 6.68 (d, J = 8 Hz, 1H), 6.89 (s, 1H), 6.94 (s , 2H), 7.18 (dd, J = 2 Hz, 8 Hz, 1H), 7.46 (d, J = 2 Hz, 1H).
(3) Synthesis of 4-tert-butyl-6- [1- (3, 5-dimethylphenyl) -1-methylethyl] -2-hydroxymethylphenol
In a 100 mL four-necked flask purged with nitrogen, 1.9 g (6.5 mmol) of 4-tert-butyl-2- [1- (3,5-dimethylphenyl) -1-methylethyl] phenol and 1.3 g (13 mmol) of magnesium chloride Paraformaldehyde (0.98 g, 33 mmol) and tetrahydrofuran (38 g) were added. To this was added 1.8 mL (13 mmol) of triethylamine, and the mixture was heated to reflux for 100 minutes. The reaction solution was allowed to cool to room temperature, and the insoluble material was filtered off. After distilling off volatile components from the filtrate under reduced pressure, ethyl acetate and 2% HCl were added to the residue. The organic layer was washed with water and saturated brine in that order and dried over anhydrous magnesium sulfate. By distilling off the solvent under reduced pressure, 2.2 g of a mixture containing 5-tert-butyl-3- [1- (3, 5-dimethylphenyl) -1-methylethyl] salicylaldehyde (yield> 99%) Got.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.37 (s, 9H), 1.71 (s, 6H), 2.26 (s, 6H), 6.79 (s, 2H), 6.81 (s, 1H), 7.39 (s, 1H), 7.72 (s, 1H), 9.83 (s, 1H), 11.2 (s, 1H).
To a 200-mL four-necked flask purged with nitrogen, 2.5-mL of the above mixture, 40-mL of tetrahydrofuran, and 20-mL of methanol were added and cooled on ice. To this was slowly added 180 mg (4.8 mmol) of sodium borohydride, and the mixture was warmed to room temperature and stirred for 15 hours. After the volatile component was distilled off from the reaction solution under reduced pressure, 2 M HCl and ethyl acetate were added. The extract was washed with saturated brine and dried over anhydrous magnesium sulfate. The obtained colorless oil was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 6 to 1: 4) to give 4-tert-butyl-6- [1- (3,5-dimethyl Phenyl) -1-methylethyl] -2-hydroxymethylphenol (2.2 g, yield: 86%) was obtained as a colorless oil.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.35 (s, 9H), 1.66 (s, 6H), 2.24 (t, J = 6 Hz, 1H), 2.28 (s, 6H), 4.62 (d, J = 6 Hz, 2H), 5.26 (s, 1H ), 6.89 (s, 1H), 6.93 (s, 2H), 7.12 (s, J = 2 Hz, 1H), 7.43 (s, J = 2 Hz, 1H).
(4) Synthesis of 5-tert-butyl-3- [1- (3,5-dimethylphenyl) -1-methylethyl] -2-hydroxybenzyl bromide
In a 100 mL 4-neck flask purged with nitrogen, add 2.2 tertg (6.8 mmol) of 4-tert-butyl-6- [1- (3,5-dimethylphenyl) -1-methylethyl] -2-hydroxymethylphenol and dichloromethane. 30 mL was added. A mixed solution (4.1 mmol) of dichloromethane (2 ジクロロメタン mL) and phosphorus tribromide (0.43 mL) was added thereto, and the mixture was stirred at room temperature for 3 hours. The reaction solution was added to ice water, and the organic layer was washed twice with saturated brine. After drying the organic layer over anhydrous magnesium sulfate, the volatile components are distilled off under reduced pressure to give 5-tert-butyl-3- [1- (3, 5-dimethylphenyl) -1-methylethyl bromide] 2.8 g (-2-99% yield) of 2-hydroxybenzyl was obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.35 (s, 9H), 1.65 (s, 6H), 2.28 (s, 6H), 4.48 (s, 2H), 6.91 (s, 1H), 6.94 (s, 2H), 7.23 (s, J = 2 Hz , 1H), 7.46 (s, J = 2 Hz, 1H).
(5) Synthesis of trans-1,2-bis {5-tert-butyl-3- [1- (3,5-dimethylphenyl) -1-methylethyl] -2-hydroxybenzylsulfanyl} cyclooctane
A 100-mL four-necked flask purged with nitrogen was charged with tert5-tert-butyl-3- [1- (3,5-dimethylphenyl) -1-methylethyl] -2-hydroxybenzyl 1.8 g (4.7 mmol), trans -Cyclooctane-1,2-dithiol 0.42 g (2.4 mmol) and tetrahydrofuran 30 mL were added and cooled on ice. Triethylamine トリ 1.0 mL (7.2 mmol) was added thereto and stirred at room temperature for 15.5 hours. The reaction solution was filtered, and volatile components were distilled off from the filtrate under reduced pressure. Ethyl acetate and aqueous ammonium chloride solution were added to the resulting residue. The organic layer was further washed with an aqueous ammonium chloride solution and saturated brine in that order, and then dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, it was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 40-1: 20) to obtain trans-1,2-bis {5-tert-butyl 2-hydroxy-3- [1- (3,5-dimethylphenyl) -1-methylethyl] benzylsulfanyl} cyclooctane and trans-1- {5-tert-butyl-2-hydroxy-3- [1- 1.7 g of a 7: 3 mixture with (3,5-dimethylphenyl) -1-methylethyl] benzylsulfanyl} -2-sulfanylcyclooctane was obtained. This mixture and 0.5- および -tert-butyl-3- [1- (3, 5-dimethylphenyl) -1-methylethyl] -2-hydroxybenzyl bromide bromide were dissolved in 20 mL of tetrahydrofuran and iced. Chilled. Triethylamine 0.25 mL (1.8 mmol) was added thereto and stirred for 21.5 hours. The reaction solution was filtered, and volatile components were distilled off from the filtrate under reduced pressure. Ethyl acetate and an aqueous ammonium chloride solution were added to the obtained residue, and the organic layer was further washed with an aqueous ammonium chloride solution and saturated brine in this order. The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 40), whereby trans-1,2-bis {5-tert-butyl-3- [1- (3, Thus, 1.8 g (yield: 94%) of 5-dimethylphenyl) -1-methylethyl] -2-hydroxybenzylsulfanyl} cyclooctane was obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.2 ~ 2.0 (m, 42H), 2.25 (s, 12H), 2.64 (brs, 2H), 3.67 (s, 4H), 5.56 (s, 2H), 6.82 (s, 2H), 6.86 (s, 4H) , 7.09 (d, J = 2 Hz, 2H), 7.36 (d, J = 2 Hz, 2H).
(Reference Example 35)
Synthesis of {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (1- (3, 5-dimethylphenyl) -1-methylethyl) benzylsulfanyl]} dichlorohafnium
In a glove box under a nitrogen atmosphere, trans-1,2-bis {5-tert-butyl-3- [1- (3, で 5-dimethylphenyl) -1-methylethyl] -2- Hydroxybenzylsulfanyl} cyclooctane 1.0 g (1.3 mmol) in toluene (5 溶液 mL) to dichloro {1,1'-oxybis [ethane] [bis (phenylmethyl) hafnium]} 640 mg (1.3 mmol) in toluene (1.3 mmol) 5 mL) solution was added dropwise at room temperature. After stirring for 1 hour, volatile components were distilled off under reduced pressure. The obtained residue was washed with pentane and dried under reduced pressure to obtain {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (1- (3,5 -Dimethylphenyl) -1-methylethyl) benzylsulfanyl]} dichlorohafnium-1.1 g (yield: 81%) was obtained as a white powder.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.73 ~ 1.7 (m, 36H), 1.96 (s, 6H), 2.08 (brs, 2H), 2.21 (s, 12H), 3.53 (d, J = 14 Hz, 4H), 4.05 (d, J = 14 Hz , 4H), 6.72 (s, 2H), 6.83 (d, J = 2 Hz, 2H), 6.90 (s, 4H), 7.51 (d, J = 2 Hz, 2H).
(Reference Example 36)
Synthesis of trans-1,2-bis {5-tert-butyl-3- [1- (4-dibenzofuranyl) -1-methylethyl] -2-hydroxybenzylsulfanyl} cyclooctane
(1) Synthesis of 1- (4-dibenzofuranyl) -1-methylethanol
To a 100 mL 4-neck flask purged with nitrogen, 8 mL of hexane and 1.0 μg (6.0 μmmmol) of dibenzofuran were added. Tetramethylethylenediamine 1.0 mL (6.7 、 mmol) and s-butyllithium 6.5 mL (1.0 M cyclohexane, hexane solution, 6.5 mmol) were added thereto and stirred for 19 hours. After further adding 18 mL of THF and cooling to −65 ° C., 2.2 mL (30 mL) of acetone was added dropwise. The mixture was warmed to room temperature and stirred for 6.5 hours, and then poured into 20 g of ice water. To this was added 2% HCl and ethyl acetate. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. After drying over anhydrous magnesium sulfate, volatile components were distilled off under reduced pressure. The obtained orange oil was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 20-1: 10) to give 1.1 g of 1- (4-dibenzofuranyl) -1-methylethanol (yield) 79%) was obtained as a colorless oil.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.82 (s, 6H), 2.73 (s, 1H), 7.30-7.38 (m, 2H), 7.44-7.49 (m, 1H), 7.54-7.62 (m, 2H), 7.85-7.88 (m, 1H), 7.95-7.97 (m, 1H).
(2) Synthesis of 4-tert-butyl-2- [1- (4-dibenzofuranyl) -1-methylethyl] phenol
1- (4-Dibenzofuranyl) -1-methylethanol 7.3 g (32 mmol), 4-tert-butylphenol 9.7 g (65 mmol), and heptane 280 mL were added to a nitrogen-substituted 500 mL flask. To this was added 140 mg (0.81 mmol) of p-toluenesulfonic acid, the temperature was raised to 100 ° C., and the mixture was stirred for 20 hours. After the reaction solution was cooled to room temperature, water and ethyl acetate were added. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate, and then the volatile component was distilled off under reduced pressure. The resulting pale orange solid was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 50-1: 20) to give 4-tert-butyl-2- [1- (4-dibenzofuranyl) There was obtained 6.7 g (yield 58%) of -1-methylethyl] phenol as a colorless solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.40 (s, 9H), 1.96 (s, 6H), 4.30 (s, 1H), 6.57 (d, J = 8 Hz, 1H), 7.11-7.91 (m, 9H).
(3) Synthesis of 4-tert-butyl-6- [1- (4-dibenzofuranyl) -1-methylethyl] -2-hydroxymethylphenol
In a 200 mL four-necked flask purged with nitrogen, 4.6 g (13 mmol) of 4-tert-butyl-2- [1- (4-dibenzofuranyl) -1-methylethyl] phenol, 2.4 g (25 mmol) of magnesium chloride, 1.9 g (64 ホルムアルデヒド mmol) of paraformaldehyde and 75 mL of tetrahydrofuran were added. To this was added 3.5 mL (25 mmol) of triethylamine, and the mixture was heated to reflux for 3 hours. The reaction solution was allowed to cool to room temperature, and the insoluble material was filtered off. After distilling off volatile components from the filtrate under reduced pressure, ethyl acetate and 2% HCl were added to the residue. The organic layer was washed with water and saturated brine in that order and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure. The resulting pale yellow solid was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 50) to give 5-tert-butyl-3- [1- (4-dibenzofuranyl) -1- Methylethyl] salicylaldehyde 4.5 g (yield 92%) was obtained as a colorless solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.41 (s, 9H), 1.99 (s, 6H), 7.25-8.00 (m, 9H), 9.75 (s, 1H), 11.2 (s, 1H).
To a 300-mL four-necked flask purged with nitrogen, 4.5 mL of the above mixture, 60 mL of tetrahydrofuran, and 30 mL of methanol were added and ice-cooled. To this was slowly added 270 mg (7.1 mmol) of sodium borohydride, and the mixture was warmed to room temperature and stirred for 14.5 hours. After distilling off volatile components from the reaction solution under reduced pressure, 2% HCl and ethyl acetate were added. The extract was washed with saturated brine and dried over anhydrous magnesium sulfate. The resulting colorless solid was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 4 to 1: 1) to give 4-tert-butyl-6- [1- (4-dibenzofuranyl) -1-methylethyl] -2-hydroxymethylphenol 4.4 g (yield 96%) was obtained as a colorless solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.38 (s, 9H), 1.97 (s, 6H), 2.00 (t, J = 6 Hz, 1H), 4.62 (d, J = 6 Hz, 2H), 6.24 (s, 1H), 6.98 (d, J = 2 Hz, 1H), 6.97-7.85 (m, 8H).
(4) Synthesis of tert-butyl-3- [1- (4-dibenzofuranyl) -1-methylethyl] -2-hydroxybenzyl bromide
In a 100-mL four-necked flask purged with nitrogen, add 4-tert-butyl-6- [1- (4-dibenzofuranyl) -1-methylethyl] -2-hydroxymethylphenol 4.4 g (11 mmol) and dichloromethane 50 mL Was added. A mixed solution (6.8 mmol) of 3 mL of dichloromethane and 0.72 mL of phosphorus tribromide was added thereto and stirred at room temperature for 3.5 hours. The reaction solution was added to ice water, and the organic layer was washed with saturated brine. After drying the organic layer over anhydrous magnesium sulfate, the volatile components are distilled off under reduced pressure to give tert-butyl-3- [1- (4-dibenzofuranyl) -1-methylethyl bromide]- 5.1 g (2-99% yield) of 2-hydroxybenzyl was obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
1.43 (s, 9H), 1.95 (s, 6H), 4.40 (s, 2H), 6.97-7.85 (m, 9H).
(4) Synthesis of trans-1,2-bis {5-tert-butyl-3- [1- (4-dibenzofuranyl) -1-methylethyl] -2-hydroxybenzylsulfanyl} cyclooctane
To a 100 mL 4-necked flask purged with nitrogen, add 1.9 g (4.3 mmol) of trans-tert-butyl-3- [1- (4-dibenzofuranyl) -1-methylethyl] -2-hydroxybenzyl bromide, trans- Cyclooctane-1,2-dithiol 0.38 g (2.1 mmol) and tetrahydrofuran 30 mL were added and ice-cooled. To this was added 0.9 mL (6.5 mmol) of triethylamine, and the mixture was stirred at room temperature for 15 hours. The reaction solution was filtered, and volatile components were distilled off from the filtrate under reduced pressure. Ethyl acetate and aqueous ammonium chloride solution were added to the resulting residue. The organic layer was further washed with an aqueous ammonium chloride solution and saturated brine in that order, and then dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, it was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 20) to obtain trans-1,2-bis {5-tert-butyl-2-hydroxy -3- [1- (4-Dibenzofuranyl) -1-methylethyl] benzylsulfanyl} cyclooctane and trans-1- {5-tert-butyl-2-hydroxy-3- [1- (4-dibenzofuran 1.8 g of a 7: 3 mixture with (nyl) -1-methylethyl] benzylsulfanyl} -2-sulfanylcyclooctane was obtained. This mixture and 0.55 g (1.2 mmol) of 5-tert-butyl-3- [1- (4-dibenzofuranyl) -1-methylethyl] -2-hydroxybenzyl bromide were dissolved in 30 mL of tetrahydrofuran and cooled on ice. did. Triethylamine 0.23 mL (1.7 mmol) was added here, and it stirred for 16 hours. The reaction solution was filtered, and volatile components were distilled off from the filtrate under reduced pressure. Ethyl acetate and an aqueous ammonium chloride solution were added to the obtained residue, and the organic layer was further washed with an aqueous ammonium chloride solution and saturated brine in this order. The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 40), whereby trans-1,2-bis {5-tert-butyl-3- [1- (4- Dibenzofuranyl) -1-methylethyl] -2-hydroxybenzylsulfanyl} cyclooctane (1.8 g, yield: 92%) was obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.61 ～ 1.6 (m, 30H), 1.92 (s, 12H), 1.99 (brs, 2H), 3.42 (d, J = 14 Hz, 2H), 3.53 (d, J = 14 Hz, 2H), 6.06 (s , 2H), 6.85 (d, J = 2 Hz, 2H), 7.19 (d, J = 2 Hz, 2H), 7.29 (m, 8H), 7.44-7.55 (m, 2H), 7.62-7.64 (m, 2H), 7.70-7.73 (m, 2H), 7.79-7.82 (m, 2H).
(Reference Example 37)
Synthesis of {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (1- (4-dibenzofuranyl) -1-methylethyl) benzylsulfanyl]} dichlorohafnium
Trans-1,2-bis {5-tert-butyl-3- [1- (4-dibenzofuranyl) -1-methylethyl] -2-hydroxybenzyl in a 100 mL Schlenk tube in a glove box under nitrogen atmosphere Sulfanyl} cyclooctane 180 mg (0.20 mmol) in toluene (1 mL) solution, dichloro {1,1'-oxybis [ethane] [bis (phenylmethyl) hafnium]} 100 mg (0.20 mmol) in toluene (1 mL) ) The solution was added dropwise at room temperature. After stirring for 1 hour, volatile components were distilled off under reduced pressure. The obtained residue was washed with pentane and dried under reduced pressure to obtain {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (1- (4-dibenzo Furanyl) -1-methylethyl) benzylsulfanyl]} dichlorohafnium 210 mg (yield 90%) was obtained as a white powder.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
-0.20-1.5 (m, 32H), 1.83 (s, 6H), 1.98 (s, 6H), 3.27 (d, J = 14 Hz, 2H), 3.87 (d, J = 14 Hz, 2H), 6.74 ( s, 2H), 7.0-7.9 (m, 16H).
(Reference Example 38)
Synthesis of trans-1,2-bis (5-tert-butyl-3- (1-ethyl-1-phenylpropyl) -2-hydroxybenzylsulfanyl) cyclooctane
(1) Synthesis of 1-ethyl-1-phenylpropanol
To a 500-mL four-necked flask purged with nitrogen, 180 mL of THF and 37 mL of phenyllithium (1.6 M dibutyl ether solution, 59 mol mmol) were added. After cooling to −63 ° C., 22 mL (210 mmol) of 3-pentanone was added dropwise. After warming to room temperature and stirring for 5.5 hours, it was poured into 200 g of ice water. To this, 2% HCl and ethyl acetate were added. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. After drying over anhydrous magnesium sulfate, volatile components were distilled off under reduced pressure. The obtained orange oil was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 20) to obtain 8.7 kg of 1-ethyl-1-phenylpropanol (yield: 89%) as a light yellow oil. It was.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.759 (t, J = 7 Hz, 6H),) 1.65 (s, 1H), 1.86 (m, 4H), 7.20-7.25 (m, 1H), 7.31-7.39 (m, 4H).
(2) Synthesis of 4-tert-butyl-2- (1-ethyl-1-phenylpropyl) phenol
To a 500-mL flask purged with nitrogen, 19 g (120 mmol) of 1-ethyl-1-phenylpropanol, 18 g (120 mmol) of 4-tert-butylphenol, and 200 mL of methylene chloride were added. The mixture was cooled in an ice bath, sulfuric acid (6.3 mL, 120 mmol) was added, and the mixture was warmed to room temperature and stirred for 20.5 hours. Furthermore, it heated up to 35 degreeC and stirred for 8.5 hours. The reaction solution was cooled to room temperature and then poured into a 5% aqueous sodium hydrogen carbonate solution. Ethyl acetate was added and the organic layer was dried over anhydrous magnesium sulfate, and then volatile components were distilled off under reduced pressure. The resulting dark orange oil is purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 40-1: 20) to give 4-tert-butyl-2- (1-ethyl-1-phenylpropyl) 7.4 g of phenol (yield 21%) was obtained as a colorless solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.599 (t, J = 7 Hz, 6H), 1.35 (s, 9H), 2.02-2.10 (m, 2H), 2.16-2.23 (m, 2H), 4.20 (s, 1H), 6.65 (d, J = 8 Hz, 1H), 7.14-7.44 (m, 7H).
(3) Synthesis of 4-tert-butyl-6- (1-ethyl-1-phenylpropyl) -2-hydroxymethylphenol
In a 200 mL four-necked flask purged with nitrogen, 5.0 -g (17 mmol) of 4-tert-butyl-2- (1-ethyl-1-phenylpropyl) phenol, 3.2 g (34 mmol) of magnesium chloride, 2.6 g of paraformaldehyde (85 mmol) and 65 mL of tetrahydrofuran were added. To this was added 4.7 mL (34 mmol) of triethylamine, and the mixture was heated to reflux for 2 hours. The reaction solution was allowed to cool to room temperature, and the insoluble material was filtered off. After distilling off volatile components from the filtrate under reduced pressure, ethyl acetate and 1M HCl were added to the residue. The organic layer was washed with water and saturated brine in that order and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 5.8 g of a mixture containing 5-tert-butyl-3- (1-ethyl-1-phenylpropyl) salicylaldehyde (yield> 99%).
¹H-NMR (400 MHz, δ, ppm, CDCD₃₎
0.600 (t, J = 7 Hz, 6H), 1.37 (s, 9H), 1.99 (s, 6H), 2.01-2.06 (m, 2H), 2.39-2.44 (m, 2H), 7.12-7.38 (m, 6H), 7.77 (d, J = 2 Hz, 1H), 9.80 (s, 1H), 11.2 (s, 1H).
To a 200-mL four-necked flask purged with nitrogen, 5.8 g of the above mixture, 30-mL of tetrahydrofuran, and 30-mL of methanol were added and cooled on ice. To this was slowly added 640 mg (17 mmol) of sodium borohydride, and the mixture was warmed to room temperature and stirred for 17.5 hours. Volatile components were distilled off from the reaction solution under reduced pressure, and 1M HCl and ethyl acetate were added. The extract was washed with saturated brine and dried over anhydrous magnesium sulfate. The obtained colorless solid was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 9 to 1: 4) to give 4-tert-butyl-6- (1-ethyl-1-phenylpropyl) ) -2-hydroxymethylphenol 4.8 g (yield: 86%) was obtained as a colorless oil.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.594 (t, J = 7 Hz, 6H), 1.34 (s, 9H), 2.01-2.09 (m, 2H), 2.19-2.27 (m, 2H), 4.59 (d, J = 6 Hz, 2H), 5.18 (s, 1H), 7.10 (d, J = 2 Hz, 1H), 7.23-7.34 (m, 5H), 7.41 (d, J = 2 Hz, 1H).
(4) Synthesis of tert-butyl-3- (1-ethyl-1-phenylpropyl) -2-hydroxybenzyl bromide
4-tert-Butyl-6- (1-ethyl-1-phenylpropyl) -2-hydroxymethylphenol 4.8 g (15 mmol) and dichloromethane 28 mL were added to a nitrogen-substituted 200 mL four-necked flask. A mixed solution (8.7 mmol) of 4 mL of dichloromethane and 0.92 mL of phosphorus tribromide was added thereto, and the mixture was stirred at room temperature for 3 hours. The reaction solution was added to ice water, and the organic layer was washed with saturated brine. After drying the organic layer over anhydrous magnesium sulfate, the volatile components are distilled off under reduced pressure to give 5.6tertg 5-tert-butyl-3- (1-ethyl-1-phenylpropyl) -2-hydroxybenzyl bromide (Yield 99%) was obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.589 (t, J = 7 Hz, 6H), 1.35 (s, 9H), 2.01-2.07 (m, 2H), 2.17-2.23 (m, 2H), 4.46 (s, 2H), 7.21 (d, J = 2 Hz, 1H), 7.27-7.36 (m, 5H), 7.42 (d, J = 2 Hz, 1H).
(5) Synthesis of trans-1,2-bis [5-tert-butyl-3- (1-ethyl-1-phenylpropyl) -2-hydroxybenzylsulfanyl] cyclooctane
In a 100 mL four-necked flask purged with nitrogen, tert5-tert-butyl-3- (1-ethyl-1-phenylpropyl) -2-hydroxybenzyl bromide 1.6 g (4.2 mmol), trans-cyclooctane-1,2 -0.36 g (2.0 mmol) of dithiol and 28 mL of tetrahydrofuran were added and ice-cooled. To this, triethylamine 0.85 mL (6.1 mmol) was added and stirred at room temperature for 21.5 hours. The reaction solution was filtered, and volatile components were distilled off from the filtrate under reduced pressure. Ethyl acetate and aqueous ammonium chloride solution were added to the resulting residue. The organic layer was further washed with an aqueous ammonium chloride solution and saturated brine in that order, and then dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, it was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 20) to obtain trans-1,2-bis [5-tert-butyl-2-hydroxy -3- (1-ethyl-1-phenylpropyl)] cyclooctane and trans-1- [5-tert-butyl-2-hydroxy-3- (1-ethyl-1-phenylpropyl) benzylsulfanyl] -2- 1.5 g of a 7: 3 mixture with sulfanylcyclooctane was obtained. This mixture and 0.50 g (1.3 mmol) of 5-tert-butyl-3- (1-ethyl-1-phenylpropyl) -2-hydroxybenzyl bromide were dissolved in 28 ml of tetrahydrofuran and cooled on ice. To this was added 0.25 mL (1.8 mmol) of triethylamine, and the mixture was stirred for 16.5 hours. The reaction solution was filtered, and volatile components were distilled off from the filtrate under reduced pressure. Ethyl acetate and an aqueous ammonium chloride solution were added to the obtained residue, and the organic layer was further washed with an aqueous ammonium chloride solution and saturated brine in this order. The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 40 to 1:20), whereby trans-1,2-bis [5-tert-butyl-3- (1 -Ethyl-1-phenylpropyl) -2-hydroxybenzylsulfanyl] cyclooctane (1.5 g, yield: 96%) was obtained as a white solid.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.571 (t, J = 7 Hz, 12H), 1.1 ~ 1.9 (m, 30H), 1.97-2.05 (m, 4H), 2.24-2.55 (m, 4H), 2.56 (brs, 2H), 3.36 (s, 4H), 5.51 (s, 2H), 7.04 (d, J = 2 Hz, 2H), 7.14-7.25 (m, 10H), 7.36 (d, J = 2 Hz, 2H).
(Reference Example 39)
Synthesis of {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (1-ethyl-1-phenylpropyl) benzylsulfanyl]} dichlorohafnium
In a glove box under a nitrogen atmosphere, trans-1,2-bis [5-tert-butyl-3- (1-ethyl-1-phenylpropyl) -2-hydroxybenzylsulfanyl] cyclooctane 160 mg in a 100 mL Schlenk tube To a solution of (0.20 トルエン mmol) in toluene (1 mL), dichloro {1,1'-oxybis [ethane] [bis (phenylmethyl) hafnium]} 100 mg (0.20 mmol) in toluene (1 mL) is added dropwise at room temperature did. After stirring for 1 hour, volatile components were distilled off under reduced pressure. The obtained residue was washed with pentane and dried under reduced pressure to give {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (1-ethyl-1- Phenylpropyl) benzylsulfanyl]} dichlorohafnium 140 mg mg (yield 67%) was obtained as a white powder.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.50-2.1 (m, 46H), 2.15 (brs, 2H), 2.42 (brs, 2H), 2.85 (brs, 2H), 3.55 (d, J = 14 Hz, 2H), 4.10 (d, J = 13 Hz , 2H), 6.82 (d, J = 2 Hz, 2H), 7.04-7.26 (m, 10H), 7.51 (d, J = 2 Hz, 2H).
(Reference Example 40)
Synthesis of trans-1,2-bis [5-methyl-2-hydroxy-3- (triphenylsilyl) benzylsulfanyl] cyclooctane
(1) Synthesis of 2-hydroxy-5-methyl-3- (triphenylsilyl) benzaldehyde
Non-patent literature: synthesized by the method described in Thadani, A. N .; Huang, Y .; Rawal, V. H. Org.Lett. 2007, 9, 3873-3876.
(2) Synthesis of 3-triphenylsilyl-5-methyl-2-hydroxybenzyl alcohol
2-Hydroxy-5-methyl-3- (triphenylsilyl) benzaldehyde (6.68 g, 16.9 mmol) was dissolved in 20 ml of tetrahydrofuran and cooled to 0 ° C. Thereto was added lithium aluminum hydride 833.8 mg (22.0 mmol), followed by stirring at 0 ° C for 15 hours. Dilute hydrochloric acid and diethyl ether were added thereto, and the ether layer was washed with water and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to quantitatively obtain the title compound (6.60 g) as colorless crystals.
¹H NMR (300 MHz, δ, ppm, CDCl_Three)
2.17 (s, 3H), 4.79 (d, J = 10 Hz, 1H), 6.75 (s, 1H), 6.95 (d, J = 4 Hz, 1H), 7.02 (d, J = 3 Hz, 1H), 7.34-7.46 (m, 9H), 7.60-7.63 (m, 6H).
¹³C NMR (100.6 MHz, δ, ppm, CDCl_Three)
20.6, 64.4, 120.4, 124.9, 128.0, 129.2, 129.7, 131.5, 134.3, 136.5, 138.3, 158.9.
(3) Synthesis of trans-1,2-bis (2-hydroxy-3-triphenylsilyl-5-methylbenzylsulfanyl) cyclooctane
In an argon atmosphere, 1.89 g (4.75 mmol) of 3-triisopropylsilyl-5-methyl-2-hydroxybenzyl alcohol was dissolved in 35 mL of tetrahydrofuran and cooled to 0 ° C. To this was added 1.3 mL (9.15 mmol) of triethylamine, 0.36 mL (4.58 mmol) of methanesulfonyl chloride was added, and the mixture was stirred at 25 ° C. for 20 hours. Thereto, a solution obtained by dissolving 310.7 mg (1.76 mmol) of trans-cyclooctane-1,2-dithiol in 10 テトラヒドロフラン mL of tetrahydrofuran was transferred in a tube under an argon atmosphere, and stirred for 19 hours under heating and reflux. A saturated aqueous ammonium chloride solution and diethyl ether were added thereto, the ether layer was washed with water and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: dichloromethane) to obtain the title compound quantitatively as a pale yellow oil (1.92 g, containing a small amount of solvent).
¹H NMR (500 MHz, δ, ppm, CDCl_Three)
1.23-1.97 (m, 12H), 2.12 (s, 6H), 2.72 (br s, 2H), 3.67-3.77 (m, 4H), 6.52 (s, 2H), 6.92 (d, J = 2 Hz, 2H ), 6.96 (d, J = 2 Hz, 2H), 7.31-7.39 (m, 18H), 7.58-7.60 (m, 12H).
¹³C {¹H} -NMR (100.4 MHz, δ, ppm, CDCl_Three)
20.5, 25.8, 26.0, 31.0, 34.0, 50.2, 121.5, 122.3, 127.7, 129.3, 129.4, 133.8, 134.6, 136.3, 138.2, 158.4.
(Reference Example 41)
Synthesis of {cyclooctanediyl-trans-1,2-bis [5-methyl-2-oxoyl-3- (triphenylsilyl) benzylsulfanyl]} dichlorohafnium
Trans-1,2-bis [5-methyl-3- (triphenylsilyl) -2-hydroxybenzylsulfanyl] cyclooctane 310 mg (0.30 mmol) of toluene (100 mL Schlenk tube in a glove box under nitrogen atmosphere) To a solution of 1 [mL] dichloro [1,1'-oxybis (ethane)] [bis (phenylmethyl) hafnium] 150 [mu] mg (0.30 [mu] mmol) in toluene (1 [mu] mL) was added dropwise at room temperature. After stirring for 3 hours, volatile components were distilled off under reduced pressure. The resulting residue is washed with pentane and dried under reduced pressure to give {cyclooctanediyl-trans-1,2-bis [5-methyl-2-oxoyl-3- (triphenylsilyl)]} dichlorohafnium 290 mg mg (yield 77%) was obtained as a white powder.
¹H-NMR (400 MHz, δ, ppm, CDCD_Three)
0.75-1.7 (m, 12H), 2.12 (s, 6H), 2.15 (brs, 2H), 3.75 (d, J = 15 Hz, 2H), 4.10 (d, J = 14 Hz, 2H), 6.80 (d , J = 2 Hz, 2H), 6.88 (d, J = 2 Hz, 2H), 7.1-7.7 (m, 30H).
(Reference Example 42)
Method for preparing d-MAO (dry methylaluminoxane)
A 200 mL two-necked flask containing a stir bar equipped with a three-way cock was replaced with nitrogen, and 100 mL of PMAO-S toluene solution (aluminum content 6.1 wt%) manufactured by Tosoh Finechem Co. was measured with a syringe and put into the flask. The solution was depressurized to remove volatile components.
The obtained white solid was redissolved in 100 mL of dehydrated toluene, and then volatile components were removed under reduced pressure.
This operation was further repeated twice to obtain 14.1 g of white powder.
Example 1
The autoclave with a stirrer having an internal volume of 400 mL was vacuum-dried and replaced with argon, and then 200 mL of toluene was charged as a solvent, and the temperature of the reactor was raised to 40 ° C. After the temperature rise, the ethylene pressure was fed while adjusting the pressure to 0.6 MPa, 139 mg of d-MAO was added, and then synthesized in Reference Example 6 {cyclooctanediyl-trans-1,2-bis [3- (1 -Adamantyl) -5-methyl-2-oxoylbenzylsulfanyl]} dibenzylhafnium (1.0 mmol / L toluene solution) (0.10 mL, 0.1 μmol) was added to initiate polymerization. Polymerization was carried out for 60 minutes while maintaining the temperature at 40 ° C. About the obtained polymer, melting | fusing point, molecular weight and molecular weight distribution, intrinsic viscosity, the number of long chain branches, and the number of terminal vinyl groups were measured according to the measurement conditions mentioned above. The results are shown in Table 1.
(Example 2)
The input amount of d-MAO was 113 mg, the polymerization temperature was 0 ° C., and {cyclooctanediyl-trans-1,2-bis [3- (1-adamantyl) -5-methyl-2 synthesized in Reference Example 6]. -Oxoylbenzylsulfanyl]} dibenzylhafnium was carried out in the same manner as in Example 1 except that the amount of (1.0 mmol / L toluene solution) was 2.0 mL (2.0 μmol). The results are shown in Table 1.
(Example 3)
The autoclave with a stirrer with an internal volume of 400 mL was vacuum-dried and replaced with argon, and then 200 mL of toluene was charged as a solvent, and the temperature of the reactor was raised to 70 ° C. After raising the temperature, the ethylene pressure was fed while adjusting the pressure to 0.6 MPa, and 0.25 mL (0.25 mmol) of trinormal octylaluminum (1.0 mol / L toluene solution) was added, and then synthesized in Reference Example 6. {Cyclooctanediyl-trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-oxoylbenzylsulfanyl]} dibenzylhafnium (1.0 mmol / L toluene solution) 0.50 mL (0 Next, 0.63 mL (2.5 μmol) of triphenylcarbenium tetrakis (pentafluorophenyl) borate (4.0 μmol / mL toluene solution) was added to initiate polymerization. Polymerization was performed for 60 minutes while maintaining the temperature at 70 ° C. The results are shown in Table 1.
Example 4
d-MAO input was set to 124 mg, and {cyclooctanediyl-trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-oxoylbenzylsulfanyl]} dibenzylhafnium instead of reference example 8 [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dibenzylhafnium (0.5 mmol / L toluene solution) 0.10 mL This was carried out in the same manner as in Example 1 except that (0.05 μmol) was used. The results are shown in Table 1.
(Example 5)
The autoclave with a stirrer having an internal volume of 400 mL was vacuum-dried and replaced with argon, and then 200 mL of toluene was charged as a solvent, and the temperature of the reactor was raised to 40 ° C. After raising the temperature, the ethylene pressure was fed while adjusting to 0.6 MPa, 0.5 mL (0.5 mmol) of triisobutylaluminum (1.0 mol / L toluene solution) was added, and then synthesized in Reference Example 8 [ Cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dibenzylhafnium (0.50 μmol / mL toluene solution) 0.10 mL (0.05 μmol) Subsequently, 0.25 mL (1.0 μmol) of triphenylcarbenium tetrakis (pentafluorophenyl) borate (4.0 μmol / mL toluene solution) was added to initiate polymerization. Polymerization was carried out for 60 minutes while maintaining the temperature at 40 ° C. The results are shown in Table 1.
(Example 6)
d-MAO input was set to 120 mg, and reference example instead of {cyclooctanediyl-trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-oxoylbenzylsulfanyl]} dibenzylhafnium {Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (1,1-diphenylethyl) -2-oxoylbenzylsulfanyl]} dibenzylhafnium (0.50 mmol / (L toluene solution) The same procedure as in Example 1 was performed except that 0.20 mL (0.10 μmol) was used. The results are shown in Table 1.
(Example 7)
d-MAO input was 126 mg, and reference example instead of {cyclooctanediyl-trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-oxoylbenzylsulfanyl]} dibenzylhafnium 12 {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dibenzylhafnium (0.50 mmol / L toluene solution) It implemented like Example 1 except having used 0.20 mL (0.10 micromol). The results are shown in Table 1.
(Example 8)
The autoclave with a stirrer with an internal volume of 400 mL was vacuum-dried and replaced with argon, and then 200 mL of toluene was charged as a solvent, and the temperature of the reactor was raised to 70 ° C. After raising the temperature, the ethylene pressure was fed while adjusting to 0.6 MPa, 0.25 mL (0.25 mmol) of triisobutylaluminum (1.0 mol / L toluene solution) was added, and then synthesized in Reference Example 27 { 0.10 mL of cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium (0.02 mmol / L toluene solution) 002 μmol), followed by 0.75 mL (3.0 μmol) of triphenylcarbenium tetrakis (pentafluorophenyl) borate (4.0 μmol / mL toluene solution) to initiate polymerization. Polymerization was performed for 60 minutes while maintaining the temperature at 70 ° C. The results are shown in Table 1.
Example 9
d-MAO input was 119 mg, and instead of {cyclooctanediyl-trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-oxoylbenzylsulfanyl]} dibenzylhafnium {Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3, 5-dimethyl-1-adamantyl) -2-oxoylbenzylsulfanyl]} dichlorohafnium (0 0.5 mmol / L, toluene solution) Except that 0.20 mL (0.10 μmol) was used, the same procedure as in Example 1 was performed. The results are shown in Table 1.
(Example 10)
The polymerization temperature was 40 ° C., the amount of triisobutylaluminum charged was (1.0 mol / L toluene solution) 0.50 mL (0.50 mmol), {cyclooctanediyl-trans-1,2-bis [ 5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium (0.02 mmol / L toluene solution) was synthesized in Reference Example 14 instead of 0.10 mL (0.002 μmol) { Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3, 5-dimethyl-1-adamantyl) -2-oxoylbenzylsulfanyl]} dichlorohafnium (1.0 mmol / L, (Toluene solution) 0.20 mL (0.20 μmol) was used, and the amount of triphenylcarbenium tetrakis (pentafluorophenyl) borate charged was changed to (4. 0 μmol / mL toluene solution) The same procedure as in Example 8 was carried out except that the concentration was 0.25 mL (1.0 μmol). The results are shown in Table 1.
Example 11
The ethylene pressure was set to 1.8 MPa, the input amount of triisobutylaluminum was set to 0.50 mL (0.50 mmol) (1.0 mol / L toluene solution), {cyclooctanediyl-trans-1,2-bis [5-tert-Butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium (0.02 mmol / L toluene solution) was synthesized in Reference Example 14 instead of 0.10 mL (0.002 μmol). {Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3, 5-dimethyl-1-adamantyl) -2-oxoylbenzylsulfanyl]} dichlorohafnium (0.50 mmol / L This was carried out in the same manner as in Example 8 except that 0.20 mL (0.10 μmol) of toluene solution was used. The results are shown in Table 1.
(Example 12)
d-MAO input was set to 124 mg, and instead of {cyclooctanediyl-trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-oxoylbenzylsulfanyl]} dibenzylhafnium {Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (2-phenyl-2-butyl) -2-oxoylbenzylsulfanyl]} dichlorohafnium (0.5) synthesized in Example 16 This was carried out in the same manner as in Example 1 except that 0.20 mL (0.10 μmol) of mmol / L, toluene solution) was used. The results are shown in Table 1.
(Example 13)
The input amount of d-MAO was 117 mg, and instead of {cyclooctanediyl-trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-oxoylbenzylsulfanyl]} dibenzylhafnium [Cyclooctanediyl-trans-1,2-bis (3-tert-amyl-5-tert-butyl-2-oxoylbenzylsulfanyl)] dichlorohafnium synthesized in Example 18 (1.0 mmol / L, toluene solution) This was carried out in the same manner as in Example 1 except that 0.20 mL (0.20 μmol) was used. The results are shown in Table 1.
(Example 14)
d-MAO input was 122 mg, and instead of {cyclooctanediyl-trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-oxoylbenzylsulfanyl]} dibenzylhafnium {Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- イル (1-methyl-1-naphthylethyl) benzylsulfanyl]} dichlorohafnium (0.5) synthesized in Example 20 This was carried out in the same manner as in Example 1 except that 0.10 mL (0.050 μmol) of mmol / L, toluene solution) was used. The results are shown in Table 1.
(Example 15)
The polymerization temperature was 40 ° C., the amount of triisobutylaluminum charged was (1.0 mol / L toluene solution) 0.50 mL (0.50 mmol), {cyclooctanediyl-trans-1,2-bis [ 5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium (0.02 mmol / L toluene solution) was synthesized in Reference Example 20 instead of 0.10 mL (0.002 μmol) { Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (1-methyl-1-naphthylethyl) benzylsulfanyl]} dichlorohafnium (0.50 mmol / L, toluene solution ) 0.10 mL (0.050 μmol) was used, and the amount of triphenylcarbenium tetrakis (pentafluorophenyl) borate charged was (4. 0 μmol / mL toluene solution) The same procedure as in Example 8 was carried out except that 0.13 mL (0.52 μmol) was used. The results are shown in Table 1.
(Example 16)
The ethylene pressure was set to 1.8 MPa, the input amount of triisobutylaluminum was set to 0.50 mL (0.50 mmol) (1.0 mol / L toluene solution), {cyclooctanediyl-trans-1,2-bis [5-tert-Butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium (0.02 mmol / L toluene solution) was synthesized in Reference Example 20 instead of 0.10 mL (0.002 μmol). {Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (1-methyl-1-naphthylethyl) benzylsulfanyl]} dichlorohafnium (0.20 mmol / L, toluene Solution) 0.10 mL (0.020 μmol) was used, input amount of triphenylcarbenium tetrakis (pentafluorophenyl) borate Was carried out in the same manner as in Example 8 except that 0.13 mL (0.52 μmol) was added (4.0 μmol / mL toluene solution). The results are shown in Table 1.
(Example 17)
200 mL of hexane was used instead of 200 mL of toluene as a solvent, {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium (Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3) synthesized in Reference Example 20 instead of 0.10 mL (0.002 μmol) (0.02 mmol / L toluene solution) -(1-methyl-1-naphthylethyl) benzylsulfanyl]} dichlorohafnium (0.50 mmol / L, toluene solution), 0.10 mL (0.050 μmol) was used, triphenylcarbenium tetrakis (pentafluorophenyl) ) The amount of borate input was set to 0.13 mL (0.52 μmol) (4.0 μmol / mL toluene solution). Except it was performed in the same manner as in Example 8. The results are shown in Table 1.
(Example 18)
d-MAO input amount was set to 124 mg, and instead of {cyclooctanediyl-trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-oxoylbenzylsulfanyl]} dibenzylhafnium 22 {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (1-methylcyclohexyl) benzylsulfanyl]} dichlorohafnium (1.0 mmol / L, toluene Solution) The reaction was performed in the same manner as in Example 1 except that 0.20 mL (0.20 μmol) was used. The results are shown in Table 1.
(Example 19)
d-MAO input amount is 127 mg, instead of {cyclooctanediyl-trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-oxoylbenzylsulfanyl]} dibenzylhafnium 24, {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (2, 3-dimethyl-2-butyl) -2-oxoylbenzylsulfanyl]} dichlorohafnium (1. This was carried out in the same manner as in Example 1 except that 0.20 mL (0.20 μmol) (0 mmol / L, toluene solution) was used. The results are shown in Table 1.
(Example 20)
d-MAO input was 122 mg, and reference example instead of {cyclooctanediyl-trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-oxoylbenzylsulfanyl]} dibenzylhafnium 26 [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3-trimethylsilyl-5-methylbenzylsulfanyl)] dichlorohafnium (0.5 mmol / L, toluene solution) 0.20 mL (0 .10 μmol) was carried out in the same manner as in Example 1. The results are shown in Table 1.
(Example 21)
The d-MAO input was 73.2 mg, instead of {cyclooctanediyl-trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-oxoylbenzylsulfanyl]} dibenzylhafnium {Cyclooctanediyl-trans-1,2-bis [5-bromo-2-oxoyl-3- (1-adamantyl) benzylsulfanyl]} dichlorohafnium (1.0 合成 mmol / L, toluene solution) synthesized in Reference Example 29 This was carried out in the same manner as in Example 1 except that 0.20 mL (0.20 μmol) was used. The results are shown in Table 1.
(Example 22)
d-MAO input amount was 110 mg, and reference example instead of {cyclooctanediyl-trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-oxoylbenzylsulfanyl]} dibenzylhafnium {Cyclooctanediyl-trans-1,2-bis [2-oxoyl-3- (triisopropylsilyl) -5-methylbenzylsulfanyl]} dichlorohafnium synthesized at 31 (1.0 mmol / L, toluene solution) 0 Performed in the same manner as in Example 1 except that 20 mL (0.20 μmol) was used. The results are shown in Table 1.
(Example 23)
d-MAO input amount was 110 mg, and reference example instead of {cyclooctanediyl-trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-oxoylbenzylsulfanyl]} dibenzylhafnium {Cyclooctanediyl-trans-1,2-bis [2-oxoyl-3- (tert-butyldimethylsilyl) -5-methylbenzylsulfanyl]} dichlorohafnium (1.0 した mmol / L, toluene solution) This was carried out in the same manner as in Example 1 except that 0.20 mL (0.20 μmol) was used. The results are shown in Table 1.
(Example 24)
The d-MAO input was 120 mg, and {cyclooctanediyl-trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-oxoylbenzylsulfanyl]} dibenzylhafnium instead of {cyclooctanediyl-trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-oxoylbenzylsulfanyl]} Octanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (1- (3,5-dimethylphenyl) -1-methyl-ethyl) benzylsulfanyl]} dichlorohafnium (1. This was carried out in the same manner as in Example 1 except that 0.20 mL (0.20 μmol) (0 mmol / L, toluene solution) was used. The results are shown in Table 1.
(Example 25)
The polymerization temperature was set to 40 ° C., and {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium (0.02 mmol / (Toluene solution) Instead of 0.10 mL (0.002 μmol), {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (1- (3,5-dimethylphenyl) ) -1-Methyl-ethyl) benzylsulfanyl]} dichlorohafnium (1.0 mmol / L, toluene solution), except that 0.10 mL (0.10 μmol) was used. The results are shown in Table 1.
(Example 26)
{Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium (0.02 mmol / L toluene solution) 0.10 mL (0 .002 μmol) instead of {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (1- (3,5-dimethylphenyl) -1-methylethyl) benzylsulfanyl ]} Carried out in the same manner as in Example 8, except that 0.10 mL (0.050 μmol) of dichlorohafnium (0.50 mmol / L, toluene solution) was used. The results are shown in Table 1.
(Example 27)
The polymerization temperature was set to 40 ° C., 200 mL of hexane was used instead of 200 mL of toluene, {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (tri Instead of 0.10 mL (0.002 μmol) of phenylmethyl) benzylsulfanyl]} dichlorohafnium (0.02 mmol / L toluene solution), {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2- Oxoyl-3- (1- (3,5-dimethylphenyl) -1-methylethyl) benzylsulfanyl]} dichlorohafnium (0.50 mmol / L, toluene solution) 0.10 mL (0.050 μmol) was used Except for this, the same procedure as in Example 8 was performed. The results are shown in Table 1.
(Example 28)
The polymerization temperature was set to 40 ° C., and {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium (0.02 mmol / L Toluene solution) instead of 0.10 mL (0.002 μmol) {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (1- (4-dibenzofuranyl) 1-methylethyl) benzylsulfanyl]} dichlorohafnium (0.50 mmol / L, toluene solution) was carried out in the same manner as in Example 8 except that 0.10 mL (0.050 μmol) was used. The results are shown in Table 1.
(Example 29)
{Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium (0.02 mmol / L toluene solution) 0.10 mL (0 .002 μmol) instead of {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (1- (4-dibenzofuranyl) -1-methylethyl) benzylsulfanyl] } It carried out like Example 8 except having used 0.10 mL (0.050 micromol) of dichloro hafnium (0.50 mmol / L, toluene solution). The results are shown in Table 1.
(Example 30)
The polymerization temperature was set to 40 ° C., and {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium (0.02 mmol / (Toluene solution) Instead of 0.10 mL (0.002 μmol), {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (1-ethyl-1-phenyl-propyl) ) Benzylsulfanyl]} dichlorohafnium (0.50 mmol / L, toluene solution) 0.10 mL (0.050 μmol) was used, and the same procedure as in Example 8 was performed. The results are shown in Table 1.
(Example 31)
{Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium (0.02 mmol / L toluene solution) 0.10 mL (0 .002 μmol) instead of {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (1-ethyl-1-phenylpropyl) benzylsulfanyl]} dichlorohafnium (0. The same procedure as in Example 8 was carried out except that 0.10 mL (0.050 μmol) of 50 mmol / L toluene solution was used. The results are shown in Table 1.
(Example 32)
{Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium (0.02 mmol / L toluene solution) 0.10 mL (0 (.002 μmol) instead of {cyclooctanediyl-trans-1,2-bis [5-methyl-2-oxoyl-3- (triphenylsilyl)]} dichlorohafnium (0.050 mmol / L, toluene solution). It implemented like Example 8 except having used 20 mL (0.010 micromol). The results are shown in Table 1.
(Comparative Example 1)
d-MAO input was 92 mg, and reference example instead of {cyclooctanediyl-trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-oxoylbenzylsulfanyl]} dibenzylhafnium The same procedure as in Example 1 except that [cyclohexanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylhafnium synthesized in 2 was used. Carried out. The results are shown in Table 1.

(Example 33)
An autoclave with a stirrer having an internal volume of 400 mL was vacuum dried and replaced with argon, and then 185 mL of toluene as a solvent and 15 mL of 1-hexene as a comonomer were charged, and the temperature of the reactor was raised to 40 ° C. After raising the temperature, the ethylene pressure was fed while adjusting the pressure to 0.6 MPa, 0.5 mL (0.5 mmol) of triisobutylaluminum (1.0 mol / L toluene solution) was added, and then synthesized in Reference Example 27 { Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium (0.10 μmol / mL toluene solution) 0.10 mL (0. Then, 0.13 mL (0.52 μmol) of triphenylcarbenium tetrakis (pentafluorophenyl) borate (4.0 μmol / mL toluene solution) was added to initiate polymerization. Polymerization was carried out for 60 minutes while maintaining the temperature at 40 ° C. As a result of the polymerization, 0.51 g of ethylene / 1-hexene copolymer was obtained. About the obtained polymer, melting | fusing point, molecular weight and molecular weight distribution, intrinsic viscosity, and comonomer content were measured according to the measurement conditions mentioned above. The results are shown in Table 2.
(Example 34)
The amount of toluene was 195 mL, the amount of 1-hexene was 5 mL, and {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} Same as Example 33 except that the amount of dichlorohafnium input (0.10 μmol / mL toluene solution) 0.10 mL (0.01 μmol) was changed to 0.10 mL (0.002 μmol) (0.02 μmol / mL toluene solution) Implemented. The results are shown in Table 2.
(Example 35)
The amount of toluene was 198 mL, the amount of 1-hexene was 2 mL, and {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} Same as Example 33 except that the amount of dichlorohafnium input (0.10 μmol / mL toluene solution) 0.10 mL (0.01 μmol) was changed to 0.10 mL (0.002 μmol) (0.02 μmol / mL toluene solution) Implemented. The results are shown in Table 2.
(Example 36)
The polymerization temperature was 70 ° C., the amount of toluene was 160 mL, the amount of 1-hexene was 40 mL, the amount of triisobutylaluminum added was 0.25 mL (0.25 mmol) (1.0 mol / L toluene solution), The same procedure as in Example 33 was conducted, except that the amount of triphenylcarbenium tetrakis (pentafluorophenyl) borate was changed to 0.75 mL (3.0 μmol) (4.0 μmol / mL toluene solution). The results are shown in Table 2.
(Example 37)
The polymerization temperature was 70 ° C., and the amount of triisobutylaluminum added was (1.0 mol / L toluene solution) 0.25 mL (0.25 mmol), {cyclooctanediyl-trans-1,2-bis [5- tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium input (0.10 μmol / mL toluene solution) 0.10 mL (0.01 μmol) (0.02 μmol / mL toluene solution) ) Except 0.10 mL (0.002 μmol) and the amount of triphenylcarbenium tetrakis (pentafluorophenyl) borate input (4.0 μmol / mL toluene solution) 0.75 mL (3.0 μmol) Was carried out in the same manner as in Example 33. The results are shown in Table 2.
(Example 38)
The polymerization temperature was 70 ° C., the amount of toluene was 190 mL, the amount of 1-hexene was 10 mL, the amount of triisobutylaluminum charged was (1.0 mol / L toluene solution) 0.25 mL (0.25 mmol), {Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium input (0.10 μmol / mL toluene solution) 0. 10 mL (0.01 μmol) was changed to (0.02 μmol / mL toluene solution) 0.10 mL (0.002 μmol), and the input amount of triphenylcarbenium tetrakis (pentafluorophenyl) borate was (4.0 μmol / mL) (Toluene solution) The same as in Example 33 except that 0.75 mL (3.0 μmol) was used. It was. The results are shown in Table 2.
(Example 39)
The polymerization temperature was 70 ° C., the amount of toluene was 195 mL, the amount of 1-hexene was 5 mL, the amount of triisobutylaluminum charged was (1.0 mol / L toluene solution) 0.25 mL (0.25 mmol), {Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium input (0.10 μmol / mL toluene solution) 0. 10 mL (0.01 μmol) was changed to (0.02 μmol / mL toluene solution) 0.10 mL (0.002 μmol), and the input amount of triphenylcarbenium tetrakis (pentafluorophenyl) borate was (4.0 μmol / mL) (Toluene solution) Executed in the same manner as in Example 33 except that 0.75 mL (3.0 μmol) was used. It was. The results are shown in Table 2.
(Example 40)
The polymerization temperature was 70 ° C., the amount of toluene was 160 mL, the comonomer was 40 mL of vinylcyclohexane instead of 1 mL of 1-hexene, and the amount of triisobutylaluminum added was 0.25 mL (0. 1 mol / L toluene solution). 25 mmol) and the input amount of triphenylcarbenium tetrakis (pentafluorophenyl) borate was set to (4.0 μmol / mL toluene solution) 0.75 mL (3.0 μmol), as in Example 33 Carried out. The results are shown in Table 2.
(Example 41)
The polymerization temperature was 70 ° C., the amount of toluene was 160 mL, the amount of 1-hexene was 40 mL, the amount of triisobutylaluminum added was 0.25 mL (0.25 mmol) (1.0 mol / L toluene solution), {Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium (0.10 μmol / mL toluene solution) 0.10 mL (0 (Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) -2-oxoylbenzyl) synthesized in Reference Example 14 instead of .01 μmol) Sulfanyl]} dichlorohafnium (1.0 mmol / L, toluene solution) 0.40 mL (0.40 μmol) was used, and triphenylcarbenium teto The same procedure as in Example 33 was performed except that the amount of lakis (pentafluorophenyl) borate input was changed to 0.75 mL (3.0 μmol) (4.0 μmol / mL toluene solution). The results are shown in Table 2.
(Example 42)
The polymerization temperature was 70 ° C., the amount of toluene was 180 mL, the amount of 1-hexene was 20 mL, the amount of triisobutylaluminum charged was (1.0 mol / L toluene solution) 0.25 mL (0.25 mmol), {Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium (0.10 μmol / mL toluene solution) 0.10 mL (0 (Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) -2-oxoylbenzyl) synthesized in Reference Example 14 instead of .01 μmol) Sulfanyl]} dichlorohafnium (1.0 mmol / L, toluene solution) 0.20 mL (0.20 μmol) was used, and triphenylcarbenium teto The same procedure as in Example 33 was performed except that the amount of lakis (pentafluorophenyl) borate charged was 0.25 mL (1.0 μmol) (4.0 μmol / mL toluene solution). The results are shown in Table 2.
(Example 43)
The polymerization temperature was 70 ° C., the amount of toluene was 190 mL, the amount of 1-hexene was 10 mL, the amount of triisobutylaluminum charged was (1.0 mol / L toluene solution) 0.25 mL (0.25 mmol), {Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium (0.10 μmol / mL toluene solution) 0.10 mL (0 (Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) -2-oxoylbenzyl) synthesized in Reference Example 14 instead of .01 μmol) Sulfanyl]} dichlorohafnium (1.0 mmol / L, toluene solution) 0.20 mL (0.20 μmol) was used, and triphenylcarbenium teto The same procedure as in Example 33 was performed except that the amount of lakis (pentafluorophenyl) borate charged was 0.25 mL (1.0 μmol) (4.0 μmol / mL toluene solution). The results are shown in Table 2.
(Example 44)
The polymerization temperature was 70 ° C., the amount of toluene was 195 mL, the amount of 1-hexene was 5 mL, the amount of triisobutylaluminum charged was (1.0 mol / L toluene solution) 0.25 mL (0.25 mmol), {Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium (0.10 μmol / mL toluene solution) 0.10 mL (0 (Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) -2-oxoylbenzyl) synthesized in Reference Example 14 instead of .01 μmol) Sulfanyl]} dichlorohafnium (1.0 mmol / L, toluene solution) 0.20 mL (0.20 μmol) was used, and triphenylcarbenium tetra The same procedure as in Example 33 was performed except that the amount of kiss (pentafluorophenyl) borate was changed to 0.25 mL (1.0 μmol) (4.0 μmol / mL toluene solution). The results are shown in Table 2.
(Example 45)
The polymerization temperature was 70 ° C., the amount of toluene was 160 mL, the comonomer was 40 mL of vinylcyclohexane instead of 1 mL of 1-hexene, and the amount of triisobutylaluminum added was 0.25 mL (0. 1 mol / L toluene solution). 25 mmol), {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium (0.10 μmol / mL toluene solution) ) Synthesized in Reference Example 14 instead of 0.10 mL (0.01 μmol) {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3,5-dimethyl-1-adamantyl)] -2-oxoylbenzylsulfanyl]} dichlorohafnium (1.0 mmol / L, toluene solution) 0.40 mL (0.40 μmol) ) And the input amount of triphenylcarbenium tetrakis (pentafluorophenyl) borate was changed to 0.75 mL (3.0 μmol) (4.0 μmol / mL toluene solution), as in Example 33 Carried out. The results are shown in Table 2.
(Example 46)
The polymerization temperature was 70 ° C., 15 mL of vinylcyclohexane was used instead of 15 mL of 1-hexene as a comonomer, and the amount of triisobutylaluminum added was 0.25 mL (0.25 mmol) (1.0 mol / L toluene solution). , {Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium (0.10 μmol / mL toluene solution) 0.10 mL ( (Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) -2-oxoyl) synthesized in Reference Example 14 instead of 0.01 μmol) Benzylsulfanyl]} dichlorohafnium (1.0 mmol / L, toluene solution) 0.20 mL (0.20 μmol) was used, and The same operation as in Example 33 was performed except that the amount of rephenylcarbenium tetrakis (pentafluorophenyl) borate was changed to 0.75 mL (3.0 μmol) (4.0 μmol / mL toluene solution). The results are shown in Table 2.
(Example 47)
The polymerization temperature was 70 ° C., the amount of toluene was 195 mL, the comonomer was replaced with 15 mL of vinylcyclohexane instead of 1 mL of 1-hexene, and the input amount of triisobutylaluminum (1.0 mol / L toluene solution) was 0.25 mL (0. 25 mmol), {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium (0.10 μmol / mL toluene solution) ) Synthesized in Reference Example 14 instead of 0.10 mL (0.01 μmol) {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3,5-dimethyl-1-adamantyl)] -2-oxoylbenzylsulfanyl]} dichlorohafnium (1.0 mmol / L, toluene solution) 0.20 mL (0.20 μmol) Example 3 was carried out in the same manner as in Example 33, except that the amount of triphenylcarbenium tetrakis (pentafluorophenyl) borate used was 0.75 mL (3.0 μmol) (4.0 μmol / mL toluene solution). did. The results are shown in Table 2.
(Example 48)
The polymerization temperature was 70 ° C., the amount of toluene was 190 mL, the amount of 1-hexene was 10 mL, the amount of triisobutylaluminum charged was (1.0 mol / L toluene solution) 0.25 mL (0.25 mmol), And {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium (0.10 μmol / mL toluene solution) 0.10 mL ( (Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (1-methyl-1-naphthylethyl) benzylsulfanyl) synthesized in Reference Example 20 instead of 0.01 μmol) ]} Conducted in the same manner as in Example 33 except that 0.10 mL (0.020 μmol) of dichlorohafnium (0.20 mmol / L, toluene solution) was used. It was. The results are shown in Table 2.
(Example 49)
The polymerization temperature was 70 ° C., the amount of toluene was 195 mL, the amount of 1-hexene was 5 mL, the amount of triisobutylaluminum charged was (1.0 mol / L toluene solution) 0.25 mL (0.25 mmol), And {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium (0.10 μmol / mL toluene solution) 0.10 mL ( (Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (1-methyl-1-naphthylethyl) benzylsulfanyl) synthesized in Reference Example 20 instead of 0.01 μmol) ]} Performed in the same manner as in Example 33 except that 0.10 mL (0.020 μmol) of dichlorohafnium (0.20 mmol / L, toluene solution) was used. . The results are shown in Table 2.
(Example 50)
The polymerization temperature was 70 ° C., 15 mL of vinylcyclohexane was used instead of 15 mL of 1-hexene as a comonomer, and the amount of triisobutylaluminum added was 0.25 mL (0.25 mmol) (1.0 mol / L toluene solution). , {Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium (0.10 μmol / mL toluene solution) 0.10 mL ( (Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (1-methyl-1-naphthylethyl) benzylsulfanyl) synthesized in Reference Example 20 instead of 0.01 μmol) ]} Dichlorohafnium (0.20 mmol / L, toluene solution) 0.10 mL (0.020 μmol) was used, and The same operation as in Example 33 was performed except that the amount of rephenylcarbenium tetrakis (pentafluorophenyl) borate was changed to 0.75 mL (3.0 μmol) (4.0 μmol / mL toluene solution). The results are shown in Table 2.
(Example 51)
The polymerization temperature was 70 ° C., the amount of toluene was 195 mL, the comonomer was replaced with 15 mL of vinylcyclohexane instead of 1 mL of 1-hexene, and the input amount of triisobutylaluminum (1.0 mol / L toluene solution) was 0.25 mL (0. 25 mmol), {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium (0.10 μmol / mL toluene solution) ) Synthesized in Reference Example 20 instead of 0.10 mL (0.01 μmol) {cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (1-methyl-1- Naphthylethyl) benzylsulfanyl]} dichlorohafnium (0.20 mmol / L, toluene solution) 0.10 mL (0.020 μmol) Example 3 was carried out in the same manner as in Example 33, except that the amount of triphenylcarbenium tetrakis (pentafluorophenyl) borate used was 0.75 mL (3.0 μmol) (4.0 μmol / mL toluene solution). did. The results are shown in Table 2.
(Example 52)
The polymerization temperature was 70 ° C., the amount of toluene was 190 mL, the comonomer was 10 mL of styrene instead of 1 mL of 1-hexene, and the amount of triisobutylaluminum added (1.0 mol / L toluene solution) 0.25 mL (0.25 mmol) ), {Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium (0.10 μmol / mL toluene solution) {Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (1-methyl-1-naphthyl) synthesized in Reference Example 20 instead of 0.10 mL (0.01 μmol) Ethyl) benzylsulfanyl]} dichlorohafnium (1.0 mmol / L, toluene solution) 3.0 mL (3.0 μmol) was used, and And triphenylcarbenium tetrakis (pentafluorophenyl) borate was carried out in the same manner as in Example 33 except that 1.0 mL (4.0 μmol) (4.0 μmol / mL toluene solution) was used. The results are shown in Table 2.

(Example 53)
To a 200 mL four-necked flask, 60 mL of toluene and 30 mL of a butadiene solution (manufactured by Aldrich, toluene solution, 20 w%) were added, and the temperature was raised to 40 ° C. After raising the temperature, ethylene was fed at a flow rate of 0.3 L / min, 0.5 mL (0.5 mmol) of triisobutylaluminum 1.0 mol / L toluene solution) was added, and then synthesized in Reference Example 27 {cyclo Octanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl]} dichlorohafnium (10 μmol / mL in toluene) 4.0 mL (40 μmol), followed by Then, 15 mL (60 μmol) of triphenylcarbenium tetrakis (pentafluorophenyl) borate (4.0 μmol / mL toluene solution) was added to initiate polymerization. Polymerization was performed for 20 minutes while maintaining the temperature at 40 ° C. As a result of the polymerization, 7.2 g of an ethylene / butadiene copolymer was obtained. About the obtained polymer, melting | fusing point, molecular weight, and molecular weight distribution were measured according to the measurement conditions mentioned above. The melting point was 120.6 ° C., Aw 5,940, and Aw / An 3.8.

The present invention is useful in the field relating to the production of ethylene polymers.

Claims

A catalyst for ethylene homopolymerization or ethylene and α-olefin copolymer containing a complex represented by the following general formula (1).

(Wherein n is 2 or 3,
R 1 and R 5 are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms constituting the ring, an alkenyl group having 2 to 20 carbon atoms, Alkynyl group having 2 to 20 carbon atoms, aralkyl group having 7 to 30 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aralkyloxy group having 7 to 30 carbon atoms, aryloxy having 6 to 30 carbon atoms Group, or a hydrocarbylsilyl group having 1 to 20 carbon atoms,
R 2 to R 4 and R 6 to R 12 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms constituting the ring, carbon An alkenyl group having 2 to 20 atoms, an alkynyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, carbon Aralkyloxy group having 7 to 30 atoms, aryloxy group having 6 to 30 carbon atoms, hydrocarbylsilyl group having 1 to 20 carbon atoms, or heterocyclic having 3 to 20 carbon atoms constituting the ring Represents a compound residue,
The alkyl group, the cycloalkyl group, the alkenyl group, the aryl group, the alkoxy group, the aralkyloxy group, the aryloxy group, the hydrocarbylsilyl group, and the heterocyclic compound residue in R 1 to R 12 The group may have a substituent,
R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 9 and R 10 , and R 11 and R 12 , Each independently may be linked together to form a ring,
The two Ls are each independently a hydrogen atom, a halogen atom, an amino group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms constituting the ring, or 2 to 20 alkenyl groups, aralkyl groups having 7 to 30 carbon atoms, aryl groups having 6 to 30 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aralkyloxy groups having 7 to 30 carbon atoms, 6 carbon atoms An aryloxy group having 1 to 30 carbon atoms, a hydrocarbylsilyl group having 1 to 20 carbon atoms, a hydrocarbylamino group having 1 to 20 carbon atoms, a hydrocarbylthiolate group having 1 to 20 carbon atoms, or the number of carbon atoms Represents 1 to 20 carboxylate groups. The alkyl group, the cycloalkyl group, the alkenyl group, the aralkyl group, the aryl group, the alkoxy group, the aralkyloxy group, the aryloxy group, the hydrocarbylsilyl group, the hydrocarbylamino group in L The hydrocarbyl thiolate group and the carboxylate group may have a substituent. )
The catalyst according to claim 1, wherein R 9 to R 12 are hydrogen atoms.
The catalyst according to claim 1 or 2, further comprising a promoter component for activation.
The catalyst according to claim 3, wherein the activation promoter component is a boron compound or an organoaluminum compound.
As the boron compound, a general formula: BR 13 R 14 R 15 , a general formula: W + (BR 13 R 14 R 15 R 16 ) − , or a general formula: (V—H) + (BR 13 R 14 R 15 R The catalyst according to claim 4, comprising a boron compound represented by 16 ) - .
Wherein R 13 to R 16 are a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, a halogenated hydrocarbyl group having 1 to 20 carbon atoms, and a substituted silyl containing 1 to 20 carbon atoms. A group, an alkoxy group having 1 to 20 carbon atoms or a disubstituted amino group containing 2 to 20 carbon atoms, which may be the same or different;
W + is an inorganic or organic cation,
V is a neutral Lewis base and (VH) + is a Bronsted acid. )
The catalyst according to claim 4 or 5, comprising at least one of a cyclic aluminoxane and a linear aluminoxane as the organoaluminum compound.
The catalyst according to any one of claims 1 to 6, wherein n is 3.
R 1 and R 5 are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms constituting the ring, an aralkyl group having 7 to 30 carbon atoms, Or a hydrocarbylsilyl group having 1 to 20 carbon atoms, and the alkyl group, the cycloalkyl group, the aralkyl group, the aryl group, and the hydrocarbylsilyl group may have a substituent. The catalyst according to any one of claims 1 to 7.
The catalyst according to any one of claims 1 to 8, wherein R 2 , R 4 , R 6 and R 8 are hydrogen atoms.
R 3 and R 7 are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms constituting the ring, an aryl group having 6 to 30 carbon atoms, or a carbon atom The catalyst according to any one of claims 1 to 9, which is a hydrocarbylsilyl group having a number of 1 to 20.
The two Ls are each independently a halogen atom, an amino group, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 6 carbon atoms. The catalyst according to any one of claims 1 to 10, which is an aryloxy group having 1 to 30 carbon atoms, a hydrocarbylsilyl group having 1 to 20 carbon atoms, or a hydrocarbylamino group having 1 to 20 carbon atoms. .
R 1 and R 5 each independently represents a cycloalkyl group having 3 to 10 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a hydrocarbylsilyl group having 1 to 20 carbon atoms constituting the ring. The catalyst according to any one of claims 1 to 11, wherein the alkyl group, the aralkyl group, and the hydrocarbylsilyl group may have a substituent.
13. A method for producing an ethylene polymer, wherein ethylene is polymerized alone in the presence of the catalyst according to claim 1 or ethylene and an α-olefin are copolymerized.
14. The method for producing an ethylene polymer according to claim 13, wherein the α-olefin is a monoolefin or a diolefin.